Single-Crystal X-ray Diffraction Study of [c2] Daisy Chains and Inclusion Complexes from A1/A2-Functionalized Pillar[5]arenes with Variable Chain Lengths

Single-Crystal X-ray Diffraction Study of [c2] Daisy Chains and Inclusion Complexes from A1/A2-Functionalized Pillar[5]arenes with Variable Chain Lengths | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Single-Crystal X-ray Diffraction Study of [c2] Daisy Chains and Inclusion Complexes from A1/A2-Functionalized Pillar[5]arenes with Variable Chain Lengths Anshel Saldanha, Mickey Vinodh, Fatemeh Alipour, Rajani Krishnapillai, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8298205/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 19 Mar, 2026 Read the published version in Journal of Chemical Crystallography → Version 1 posted 9 You are reading this latest preprint version Abstract A1/A2-Asymmetric difunctionalized pillar[ 5 ]arenes bearing either n-decyloxy and propargyloxy groups or n-octyloxy and propargyloxy groups are synthesized and investigated for their supramolecular assembly behavior under different crystallization conditions. Distinct crystal systems are obtained depending on the co-crystallization medium. Host–guest inclusion complexes with adiponitrile form when crystallization is carried out from solutions containing adiponitrile, whereas cyclic [ c2 ] daisy chain (“double-threaded dimer”) architectures are produced from mixed chloroform/cyclohexane solutions. The resulting supramolecular assemblies are characterized by single crystal X-ray diffraction and Hirshfeld surface analyses. Variation in alkyl chain length (n-decyloxy versus n-octyloxy) on the pillar[ 5 ]arene framework exerts a pronounced effect on the non-covalent interactions and the consequent self-assembly modes within the crystal networks. di-functionalized pillar[5]arenes double-threaded dimers inclusion complexes supramolecular assembly Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Introduction Pillar[ 5 ]arene-based macrocycles have attained significant attention owing to their highly symmetrical, rigid architectures and electron-rich cavities, which render them excellent candidates for molecular recognition and host–guest interactions [ 1 – 5 ]. Functionalization of pillar[ 5 ]arenes, particularly at the macrocyclic rims, greatly enhances their structural and chemical versatility, enabling fine-tuning of their physicochemical properties, solubility, and binding affinities [ 6 – 12 ]. The nature and position of substituent groups at the rim play a decisive role in governing the self-assembly behavior and supramolecular characteristics of these systems. In particular, variations in the length and flexibility of alkyl chains attached to the rims can markedly influence intermolecular interactions, molecular packing, and the resulting solid-state organization [ 13 – 17 ]. Previously, we reported the crystal structures of supramolecular assemblies comprising cyclic [ c2 ] daisy chain (“double-threaded dimer”) and host-guest inclusion complexes derived from an A1/A2-10-bromodecyloxy-propargyloxy-difunctionalized pillar[ 5 ]arene [ 18 ]. The influence of crystallization solvents on the solid-state supramolecular organization of this macrocycle was elucidated in detail, revealing that both [ c2 ] daisy chain rotaxanes and host–guest inclusion complexes exhibit distinct packing motifs depending on the solvent system employed. To extend our previous investigations, we report a comparative crystallographic study of two A1/A2-asymmetric di-functionalized pillar[ 5 ]arenes, in which one macrocyclic rim bears either n-decyloxy and propargyloxy or n-octyloxy and propargyloxy substituents which are crystallized under different solvent conditions (Scheme 1 ) .This study aims to investigate the influence of the alkyl chain length on the self-assembly and supramolecular organization in the crystalline phase. The results provide valuable insights into the structure–property relationships governing the formation of functionalized pillar[ 5 ]arene-based supramolecular architectures and contribute to the rational design of new crystalline materials with tailored supramolecular features. Experimental Synthesis and crystal growth Synthesis of 1-propargyloxy-4-octyloxy benzene :: 1- propargyloxy-4-hydroxy benzene [ 19 ] (1.48 g, 10 mmol) and dry potassium carbonate (2.76 g; 20 mmol ) was dissolved in dry DMF (30 ml) and 1-bromooctane (2.70 g, 14 mmol) was added. This mixture was heated at 80 o C overnight and then water (200 mL) was added to the reaction mixture. The organic fraction was then recovered by extraction with dichloromethane (200 ml). The dichloromethane fraction was washed with water (100 mL each; 5 times) to remove any DMF solvent present and then dried over Na 2 SO 4 and did column purification using dichloromethane/hexane mixture (50:50 v/v). Yield 2.1 g (81%). 1 H NMR (400 MHz, CDCl 3 , δ): 0.92 (m, 3H), 1.33 (m, 8H), 1.48 (m, 2H), 1.78 (m, 2H), 2.52 (m, 1H), 3.92 (m, 2H), 4.66 (m, 2H), 6.86 (m, 2H), 6.93 (m, 2H). EI-MS: 260.06 [M]. Synthesis of 1-propargyloxy-4-decyloxy benzene : 1- propargyloxy-4-hydroxy benzene [ 19 ] (1.48 g, 10 mmol) and dry potassium car-bonate (2.76 g; 20 mmol ) was dissolved in dry DMF ( 30 ml) and 1-bromodecane (3.09 g, 14 mmol) was added and the reaction was proceeded similar to that of the synthesis of 1-propargyloxy-4-octyloxy benzene. Yield 2.4 g (83%). 1 H NMR (400 MHz, CDCl 3 , δ): 0.92 (m, 3H), 1.43 (m, 12H), 1.58 (m, 2H), 1.78 (m, 2H), 2.58 (m, 1H), 3.94 (m, 2H), 4.67 (m, 2H), 6.85 (m, 2H), 6.94 (m, 2H). EI-MS: 288.11 [M]. Synthesis of 1-(1-propargyloxy-4-octyloxy)-2,3,4,5- dimethoxy pillar [ 5 ] arene ( P8 ) : Paraformaldehyde (3.1 g, 100 mmol) was added to a solution of 1,4-dimethoxybenzene (4.4 g, 32 mmol) and 1-propargyloxy-4-octyloxy benzene (520 mg, 2 mmol) in dichloromethane (250 mL) under nitrogen atmosphere. Boron trifluoride diethyl etherate (4 ml, 32 mmol) was then added to the solution and the mixture was stirred at 0 o C for 1 h. Methanol (400 mL) was poured into the mixture to quench the reaction and filtered. The residue was dissolved in chloroform (100 mL) and filtered. The filtrate was concentrated to a small volume and adsorbed on silica and did column using dichloromethane : hexane mixture (60:40 v/v). The second last fraction was the intended pillar[ 5 ]arene. Yield: 387 mg (22%). 1 H NMR (400 MHz, CDCl 3 , δ): 0.81 (m, 3H), 1.12 (m, 4H), 1.28 (m, 2H), 1.34 (m, 2H), 1.51 (m, 2H), 1.80 (m, 2H), 1.93 (m, 1H), 3.69 (m, 24H), 3.80 (m, 8H), 3.82 (s, 2H), 3.90 (m, 2H), 4.40 (m, 2H), 6.76 (s, 1H), 6.77 (s, 1H), 6.79 (s, 1H), 6.81 (s, 1H), 6.82 (m, 4H), 6.84 (m, 2H). 13 C NMR (150 MHz, CDCl 3 , δ): 14.2, 22.7, 26.4, 29.4, 29.4, 29.6, 29.8, 29.8, 29.9, 30.7, 31.8, 55.9, 55.9, 56.0, 56.3, 68.9, 74.9, 79.0, 114.1, 114.2, 114.2, 114.2, 114.3, 114.4, 114.6, 115.4, 115.7, 128.2, 128.4, 128.4, 128.5, 128.6, 128.7, 128.7, 128.8, 129.0, 148.9, 150.8, 150.9, 151.0, 151.0, 151.0. HRMS (EI) m / z : [M] + calcd for C 54 H 64 O 10 , 872.4494; found, 872.4495. Synthesis of 1-(1-propargyloxy-4-decyloxy)-2,3,4,5- dimethoxy pillar [ 5 ] arene ( P10 ) : Paraformaldehyde (3.1 g, 100 mmol) was added to a solution of 1,4-dimethoxybenzene (4.4 g, 32 mmol) and 1-propargyloxy-4-decyloxy benzene (576 mg, 2 mmol) in dichloromethane (250 mL) under nitrogen atmosphere. Boron trifluoride diethyl etherate (4 ml, 32 mmol) was then added to the solution and the reaction and the product purification was carried out similar to those for the synthesis of P8 . Yield: 372 mg (21%). 1 H NMR (400 MHz, CDCl 3 , δ): 0.82 (m, 3H), 1.12 (m, 6H), 1.28 (m, 4H), 1.35 (m, 2H), 1.52 (m, 2H), 1.80 (m, 2H), 1.87 (m, 1H), 3.68 (m, 24H), 3.79 (m, 8H), 3.83 (s, 2H), 3.92 (m, 2H), 4.42 (m, 2H), 6.74 (s, 1H), 6.76 (s, 1H), 6.78 (s, 1H), 6.81 (s, 2H), 6.81 (m, 2H), 6.82 (m, 2H), 6.83 (s, 1H). 13 C NMR (150 MHz, CDCl 3 , δ): 14.1, 22.7, 22.8, 26.3, 29.4, 29.4, 29.7, 29.8, 29.9, 29.9, 30.4, 31.8, 55.8, 55.9, 56.0, 56.3, 68.8, 74.9, 79.1, 114.1, 114.1, 114.2, 114.2, 114.3, 114.5, 114.6, 115.3, 115.7, 128.2, 128.3, 128.5, 128.6, 128.7, 128.7, 128.9, 129.0, 148.9, 150.8, 150.8, 151.0, 151.0, 151.1. HRMS (EI) m / z : [M] + calcd for C 56 H 68 O 10 , 900.4807; found, 900.4809. Crystal growth : Single crystals of these pillar[ 5 ]arene systems were grown by slow evaporation of either P8 or P10 (10 mg) from 1.0 mL of chloroform/cyclohexane (8:2 v/v) or chloro-form/adiponitrile (8:2 v/v) solvent mixtures. The resulting crystals were analyzed via single-crystal X-ray diffraction. Instrumentation and crystal refinement Nuclear magnetic resonance (NMR) spectroscopy was done either by Bruker Avance II 600 MHz (Germany) or by Burker DPX 400 MHz spectrometers. Electron impact ionization (EI) mass spectrometry was performed using Thermo Scientific DFS High Resolution GC/MS (Germany) mass spectrometer. The single crystal data collection were made on Rigaku Rapid II (Japan) diffractometer by Mo-Kα radiation. The crystal data collected were processed by ‘Crystalclear’ software package. The structures were then solved by direct methods using ‘CrystalStructure’ crystallographic software package and the refinement were performed using SHELXL-2019/3. All non-hydrogen atoms were refined anisotropically and hydrogen atoms were refined using the riding model. In the P8_D crystal, the SIMU and DELU commands were used to restrain the thermal displacement parameters of the n-octyloxy chain of the pillar[ 5 ]arene, while DFIX and DANG were applied to adjust its geometry. The geometry of the propargyloxy substituent also adjusted by DFIX command. One of the solvent chloroform molecules in this crystal is disordered a special position and is refined by part − 1 command. The hydrogen atom in this diordered molecule is assaigned from the electron density map. SIMU and DELU were used to restrain thermal displacement parameters, while DFIX, DANG were employed to refine the geometry of the all chloroform molecules in this crystal. In the P10_D crystal, the SIMU and DELU commands were used to restrain the thermal displacement parameters of the n- decyloxy chain of the pillar[ 5 ]arene, while DFIX and DANG were used to adjust its geometry. In addition, DFIX, DANG were employed to refine the geometry of the cyclohexane molecule present in this crystal and SIMU and DELU were used to restrain thermal displacement parameters of these solvent atoms. In the P8·ADN crystal, DFIX and DANG were applied to refine the molecular geometry, and the SIMU and DELU commands were used to restrain the thermal displacement parameters of the n-octyloxy chain and the propargyloxy fragment of the pillar[ 5 ]arene. Furthermore, for the encapsulated adiponitrile molecule, SIMU and DELU were employed to restrain its thermal displacement parameters, while DFIX and DANG were applied to refine its geometry. In the P10·ADN crystal, the SIMU and DELU commands were applied to restrain the thermal displacement parameters, while DFIX and DANG were used to adjust the geometries of both the n- decyloxy chain of the pillar[ 5 ]arene and the adiponitrile guest molecule. The crystallographic data for the structures reported in this paper has been deposited at the Cambridge Crystallographic Data Centre (CCDC 2497292–2497295). Results and Discussion Crystal structures of A1/A2-difunctionalized pillar[ 5 ]arenes Pillar[ 5 ]arene macrocycles possess a strong tendency to encapsulate linear molecules within their electron-rich cavities. When a long, linear alkyl chain is introduced at the rim of the macrocycle, it can undergo self-inclusion into its own cavity or inter-inclusion into the cavity of a neighboring macrocycle. In contrast, the presence of a competing guest molecule prevents this intramolecular threading, causing the alkyl chain to project outward from the already occupied cavity. In our previous work, we reported the crystal structures and supramolecular self-assembly of an A1/A2-10-bromodecyloxy-propargyloxy-difunctionalized pillar[ 5 ]arene under various crystallization conditions [ 18 ]. When crystallized from chloroform or N,N-dimethylformamide (DMF), the system yielded cyclic [ c2 ] daisy chain “double-threaded dimer” assemblies. Alternatively, crystallization from a chloroform solution containing adiponitrile produced host–guest inclusion complexes. Adiponitrile, a well-established guest for pillar[ 5 ]arenes, is particularly effective due to its strong encapsulation ability [ 20 ]. Moreover, both the [ c2 ] daisy chain rotaxanes and the pillar[ 5 ]arene–adiponitrile inclusion complexes displayed distinct supramolecular packing arrangements in the crystalline state depending on the solvent employed, underscoring the critical influence of solvent environment on the solid-state assembly of functionalized pillar[ 5 ]arenes. The influence of long alkyl chain in the formation of such pillar[ 5 ]arene-adiponitrile host-guest systems or double-threaded dimer and their consequent propagation into supramolecular self-assembly requires detailed investigation. So, in this present work we designed two pillar[ 5 ]arene derivatives to explore this effect: one featuring n-decyloxy-propargyloxy groups ( P10 ) and the other with n-octyloxy-propargyloxy groups ( P8 ), both functionalized at the A1/A2 positions. This design allows us to systematically study how variations in alkyl chain length influence the supramolecular behavior of these systems. The synthesis and characterization of P8 and P10 are detailed in the Experimental Section. Single crystals of each compound were grown using two different solvent systems: chloroform/cyclohexane (8:2 v/v) and chloroform/adiponitrile (8:2 v/v). The resulting crystals were analyzed via single crystal X-ray diffraction. The crystal structures obtained from chloroform/cyclohexane (denoted as P8_D and P10_D ) and those from chloroform/adiponitrile (denoted as P8.ADN and P10.ADN ) are shown in Fig. 1 – 2 . Their corresponding crystallographic data are summarized in Supporting information ( Tables S1-S2 ). Thermal ellipsoid representations of the asymmetric units for all four crystal structures are also provided in the Supporting Information ( Fig. S1 -S4 ). The asymmetric unit of P8_D comprises one pillar[ 5 ]arene molecule and one and a half co-crystallized chloroform molecules. In contrast, the asymmetric unit of P10_D , crystallized from the same chloroform-cyclohexane solvent mixture, contains one pillar[ 5 ]arene molecule along with one co-crystallized cyclohexane molecule. Notably, in both P8_D and P10_D , the n-octyl and n-decyl chains of adjacent pillar[ 5 ]arene molecules are double-threaded into each other's cavities, giving rise to a cyclic [ c2 ] daisy chain-type supramolecular dimer. These [ c2 ] daisy chain structures- also referred to as double threaded dimers- are formed by two interpenetrated, half-note-shaped components and represent the simplest form of mechanically interlocked macrocyclic systems. Such assemblies can reversibly switch between threaded and unthreaded (open) states, making them valuable in biomimetic research and the design of artificial molecular machines and supramolecular polymers [ 21 ]. Similarly, the reversible formation of pseudo[ 1 ]rotaxane and/or double-threaded dimer can be controlled via competing guest molecules in the supramolecular systems. The formation of these dimers in both P8_D and P10_D is primarily driven by multiple C–H⋯O and C–H⋯π interactions involving the threaded alkyl chains within the macrocyclic cavities. In P8_D , the dimer formation is further stabilized by interaction through the co-crystallized chloroform molecules, which act as caps at both ends of the pillar[ 5 ]arene cavity via C–H⋯Cl contacts, as illustrated in Fig. 3 . Detailed quantitative data on the non-covalent interactions- including interaction distances and angles- are provided in Table 1 . In the case of P10_D , however, the n-decyl chains are confined within the host cavity solely through C–H⋯O and C–H⋯π interactions, without any additional stabilization from co-crystallized solvent molecules. This behavior is depicted in Fig. 4 and the quantitative data are provided in Table 2 . Table 1 Non-bonding interactions between pillar[ 5 ]arene cavity and octyloxy chain in P8_D daisy chain double-threaded dimer ( Å, o ). A-B...C A-B B...C A....C A-B...C C39 i -H39B i ⋯O2 0.97 3.079 3.88(1) 141.0 C40-H40A⋯O4 i 0.97 2.882 3.68(1) 140.1 C41-H41A⋯O10 i 0.97 3.391 4.32(1) 161.9 C41-H41B⋯O8 i 0.97 3.076 3.94(2) 148.9 C42-H42A⋯π1 i 0.97 2.937 3.900 172.33 C42-H42B⋯ π2 i 0.97 2.872 3.635 136.30 C43-H43A⋯ π5 i 0.97 3.023 3.972 166.23 C43-H43B⋯ π4 i 0.97 2.999 3.760 127.50 C44-H44A⋯O1 i 0.97 3.378 4.23(1) 147.7 C44-H44B⋯O3 i 0.97 3.124 4.07(1) 165.0 C45-H45A⋯O7 i 0.97 3.011 3.64(1) 123.4 C45-H45B⋯O5 i 0.97 3.178 4.06(2) 152.8 C46-H46C⋯Cl4 i 0.96 2.833 3.65(2) 144 Symmetry code: (i) 1.5-x, 1/2-y, 1-z; π1, π2, π4 & π5 are the centroids of the phenyl rings C1-C6, C8-C13, C22-C27 & C29-C34 respectively. Table 2 Non-bonding interactions between pillar[ 5 ]arene cavity and decayloxy chain in P10_D daisy chain double-threaded dimer ( Å, o ). A-B...C A-B B...C A....C A-B...C C39 i -H39B i ⋯O2 0.97 3.097 3.88(1) 138.9 C40-H40A⋯O4 i 0.97 2.917 3.74(1) 143.4 C41-H41B⋯O8 i 0.97 3.135 4.10(1) 176.0 C42-H42A⋯π1 i 0.97 3.066 3.922 147.90 C42-H42B⋯ π3 i 0.97 3.224 4.057 145.03 C43-H43A⋯ π4 i 0.97 2.864 3.762 154.39 C43-H43B⋯ π5 i 0.97 2.974 3.911 162.60 C44-H44A⋯O1 i 0.97 3.291 4.26(1) 173.0 C44-H44B⋯O3 i 0.97 3.219 3.97(1) 135.5 C45-H45B⋯O7 i 0.97 3.351 3.88(1) 116.0 Symmetry code: (i) 2-x, 2-y, 2-z; π1, π3, π4 & π5 are the centroids of the phenyl rings C1-C6, C15-C20, C22-C27 & C29-C34 respectively. The crystal structures of P8.ADN and P10.ADN , in which the respective pillar[ 5 ]arenes were crystallized from a chloroform–adiponitrile solvent system, show that the adiponitrile ( ADN ) molecule is encapsulated within the cavities of the pillar[ 5 ]arenes, forming host–guest inclusion complexes. Notably, no additional solvent molecules are co-crystallized within the lattice as space-filling agents. Although both pillar[ 5 ]arene systems form inclusion complexes with adiponitrile, their solid-state structural features differ slightly. In the P8.ADN crystal, the propargyloxy functional group is oriented inward toward the pillar[ 5 ]arene cavity, while the n-octyloxy chain extends outward from the macrocycle. In contrast, the P10.ADN crystal exhibits the opposite arrangement: the propargyloxy group points outward, and the n-decyloxy chain bends inward toward the macrocycle. This difference in orientation becomes especially apparent when comparing two adjacent pillararene molecules in each crystal, as illustrated in Fig. 5 . Such structural deviations significantly influence the supramolecular self-assembly within the crystal network - a topic discussed in detail in the following section. In both P8.ADN and P10.ADN systems, the adiponitrile guest is stabilized by multiple C–H⋯O and C–H⋯π interactions, as shown in Fig. 6 and summarized in Table 3 and Table 4 . Table 3 Host-guest interactions between Pillar[ 5 ]arene host and adiponitrile guest in P8.ADN crystals ( Å, o ). A-B...C A-B B...C A....C A-B...C C38-H38 ⋯N1 0.93 2.73 2.93(3) 93.8 C56-H56A⋯O5 0.97 3.102 3.99(2) 153.4 C56-H56B⋯O7 0.97 3.049 3.85(2) 141.3 C57-H57A⋯π1 0.97 3.002 3.786 138.76 C57-H57B⋯ π2 0.97 2.620 3.760 163.44 C58-H58A⋯ π4 0.97 3.081 3.940 148.33 C58-H58B⋯ π3 0.97 3.241 4.055 142.69 C59-H59A⋯O2 0.97 3.169 3.98(1) 142.5 C59-H59B⋯ π2 0.97 3.107 3.871 136.83 π1-π 4 are the centroids of the phenyl rings C1-C6, C8-C13, C15-C20 & C22-C27 respectively. Table 4 Host-guest interactions between Pillar[ 5 ]arene host and adiponitrile guest in P10.ADN crystals ( Å, o ). A-B...C A-B B...C A....C A-B...C C51-H51A ⋯N1 0.960 2.997 3.87(3) 153.26 C58-H58A⋯O9 0.97 2.888 3.81(1) 159 C58-H58B⋯O7 0.97 3.003 3.77(2) 136 C59-H59A⋯π2 0.97 3.210 3.740 116.12 C59-H59B⋯ π3 0.97 3.152 4.051 154.72 C60-H60A⋯ π5 0.97 3.124 3.750 123.63 C60-H60B⋯ π4 0.97 2.916 3.858 164.05 C61-H61A⋯O4 0.97 3.026 3.91(2) 152.8 C61-H61B⋯ π3 0.97 2.968 3.879 156.82 C54-H54A⋯N2 0.960 3.081 3.84(3) 137.30 π2-π5 are the centroids of the phenyl rings C8-C13, C15-C20, C22-C27 & C29-C34 respectively. Intermolecular non-bonding interactions The pillar[ 5 ]arene-based double-threaded dimers and 1:1 inclusion complexes studied here exhibit a variety of non-covalent interactions within their crystal networks. These non-bonding interactions - occurring at distances shorter than typical van der Waals contacts - play a crucial role in stabilizing the crystal structures. The interactions between each pillar[ 5 ]arene systems and their immediate neighboring molecules are illustrated in Fig. 7 – 10 . The intermolecular non-covalent interactions observed in the P8_D crystals are particularly noteworthy. The solvent chloroform plays an active role in stabilizing the crystal structure through various interactions, including C–H⋯π, C–H⋯O, C–H⋯Cl, and Cl⋯Cl contacts, as illustrated in Fig. 7 . Remarkably, the chloroform molecules at a given lattice position interact with four pillar[ 5 ]arene molecules of different symmetries in this crystal. Beyond the chloroform-mediated interactions, each pillar[ 5 ]arene unit also engages in direct contacts with two neighboring pillar[ 5 ]arenes via C–H⋯π and C–H⋯O interactions. The C–H⋯π interaction originates specifically from the propargyl moiety of the pillar[ 5 ]arene, as shown in Fig. 8 . The P10_D crystals exhibit a nearly identical pattern of intermolecular pillar[ 5 ]arene–pillar[ 5 ]arene interactions, involving C–H⋯π (from the propargyl end) and C–H⋯O contacts (Supporting information; Fig. S5 ). However, unlike P8_D , the P10_D crystals do not display any solvent-mediated interactions. Quantitative data on these non-covalent interactions for P8_D and P10_D crystals are provided in Tables 5 & 6 respectively. Table 5 Intermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the P8_D crystals ( Å, o ). A-B...C A-B B...C A....C A-B...C C47-H47B⋯O10 iv 0.96 2.654 3.611(1) 172.6 C38-H38⋯π5 iv 0.93 3.237 4.003 140.95 C46 iii -H46C iii ⋯Cl4 0.96 2.833 3.65(2) 144 C55-H55⋯ π4 0.98 2.323 3.298 173.75 C56-H56⋯O5 i 0.96 2.404 3.233 145 C56-Cl5⋯Cl3 i 1. 75(2) 3.23(1) 4.84(2) 152.3(8) Symmetry code: (i) 1-x, y, 1.5-z; (iii) -1/2 + x, -1/2 + y. (iv) x, -1 + y, z; π 4 and π 5 are the centroid of the phenyl rings constituting C22-C27 and C29-C34 respectively. Table 6 Intermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the P10_D crystals ( Å, o ). A-B...C A-B B...C A....C A-B...C C38-H38⋯ π5 iv 0.93 3.451 4.264 147.41 C49-H49A⋯O10 iv 0.96 2.714 3.607(9) 155.0 Symmetry code: (iv) x, 1 + y, z; π5 is the centroid of the phenyl ring constituting C29-C34. In the P8.ADN crystal, each pillar[ 5 ]arene macrocycle interacts with six neighboring pillar[ 5 ]arene molecules of different symmetries within the crystal lattice. Both the propargyloxy and n-octyloxy groups participate in these intermolecular interactions, as illustrated in Fig. 9 . Notably, two distinct types of complementary non-covalent interactions are observed in the crystal network: C–H⋯O and C–H⋯π interactions, depicted too in Fig. 9 . The quantitative details of these interactions are provided in Table 7 . Similarly, in the P10.ADN crystal, each pillar[ 5 ]arene macrocycle also engages with six other pillar[ 5 ]arene units of varying symmetry via C–H⋯π interactions, as shown in Fig. 10 and detailed in Table 8 . However, unlike P8.ADN , the propargyloxy group in P10.ADN does not participate in any significant intermolecular interactions. Therefore, P10.ADN is the only system in this study where the propargyloxy terminal group of the pillar[ 5 ]arene does not contribute meaningfully to the crystal's non-covalent contacts. Table 7 Intermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the P8.ADN crystals ( Å, o ). A-B...C A-B B...C A....C A-B...C C46-H46A⋯O10 i 0.96 2.647 3.58(2) 165.0 C49-H49B⋯ π2 v 0.96 2.953 3.848 155.60 C50-H50B⋯O8 vi 0.96 2.711 3.655(9) 167.5 C54-H54B⋯ π1 ii 0.96 2.961 3.701 134.83 Symmetry code: (i) x, 1 + y, z; (ii) 1 + x, y, z; (v) 1-x, 1-y, 1-z; (vi) 2-x, 1-y, 1-z; π1 is the centroid of C37 ≡ C38 and π2 is the centroids of the phenyl ring constituting C15-C20. Table 8 Intermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the P10.ADN crystals ( Å, o ). A-B...C A-B B...C A....C A-B...C C36-H36A⋯ π3 i 0.97 3.304 4.101 140.82 C39-H39A⋯ π4 ii 0.97 3.360 4.059 130.71 C46-H46B⋯ π5 iii 0.97 2.915 3.748 144.56 C53-H53C⋯ π1 v 0.96 3.305 4.159 149.06 Symmetry code: (i) 1 + x, -1 + y, z; (ii) x, -1 + y, z; (iii) -1 + x, y, z; (v) x, 1 + y, z; π1, π3, π4 & π5 are the centroids of the phenyl rings C1-C6,C15-C20, C22-C26 & C29-C34 respectively. The packing pattern of the P8.ADN complex reveals that the crystal network organizes into one-dimensional channels along the a-axis. Similarly, the P10.ADN complex also forms one-dimensional channels in the same direction, with only minor deviations in its packing features compared to P8.ADN . For the P8_D and P10_D dimeric systems, the packing patterns exhibit a comparable propagation of dimeric pillar[ 5 ]arene units, with the resulting channels being occupied by solvent molecules. Detailed packing features for all four pillar[ 5 ]arene systems studied in this work are provided in the Supporting Information ( Fig. S7 & Fig. S8 ). Hirshfeld surface analysis structures The non-covalent interactions present in the [ c2 ] daisy chain rotaxanes and the pillar[ 5 ]arene–adiponitrile host–guest inclusion complexes discussed in this study were further analyzed using Hirshfeld surface (HS) analysis [ 22 – 23 ]. The intermolecular interactions in the P8_D and P10_D crystals visualized through the 3D dnorm surface obtained from Hirshfeld surface analysis is given in Fig. 11 . In both crystals, the red and white regions located at the center of the macrocyclic cavities represent contacts shorter than the sum of the van der Waals radii, corresponding mainly to C–H⋯O and C–H⋯π interactions involved in the formation of the threaded dimers. Additionally, in P8_D , non-covalent interactions involving chloroform molecules are clearly visualized as in-tense red spots on the surface. Other pillar[ 5 ]arene-pillar[ 5 ]arene connection contacts are also seen in the systems as red spots and/or white regions. Hirshfeld surface analysis of P8.ADN and P10.ADN indicated host-guest non-bonding interactions between pillar[ 5 ]arene host and adiponitrile guest as white coloured regions inside the macrocyclic cavities (Supporting information; Fig. S6 ). Strong intermolecular interactions between adjacent pillar[ 5 ]arene units were also evident from the 3D dnorm of HS surfaces. To quantitatively summarize these interactions, 2D fingerprint plots were gen-erated from the HS data. From the 2D fingerprint plots, the major intermolecular interactions in the P8_D crystal are H⋯H (60.5%), C...H (21.6), O⋯H (7.0%), Cl⋯H (8.1%) and C…C (1.2%) where as for P10_D they are H⋯H (71.5%), C...H (20.7), O⋯H (6.4%) and C…C (1.3%). In the case of inclusion complexes the corresponding values are H⋯H (66.4%), C...H (20.9), O⋯H (6.6%), N⋯H (4.9%) and C…C (0.8%) (for P8.ADN ) and H⋯H (66.5%), C...H (21.2), O⋯H (6.4%), N⋯H (4.7%) and C…C (1.2%) (for P10.ADN ) respectively. These fingerprint plots provide valuable quantitative insight into the dominant types of intermolecular interactions present in each crystal structure Conclusion The synthesis and characterization of A1/A2 asymmetric difunctionalized pillar[ 5 ]arenes, bearing propargyloxy groups at one rim and either n-decyloxy or n-octyloxy groups at the other, were accomplished. Depending on the crystallization conditions, these macrocycles formed distinct supramolecular crystal architectures. In the absence of strong encapsulating ligands, pair of pillar[ 5 ]arenes assembled into cyclic [ c2 ] daisy-chain type “double-threaded dimers” formed in which the long alkyl chains threaded through each other’s cavity. When adiponitrile molecules were present in the crystallization solvent, host–guest inclusion complexes between the pillar[ 5 ]arenes and adiponitrile gave rise to extended crystal networks. The resulting supramolecular assemblies were thoroughly characterized by single-crystal X-ray diffraction and Hirshfeld surface analysis. Results revealed that the alkyl chain length on the pillar[ 5 ]arene skeleton influenced the structural features, noncovalent interactions, and self-assembly behavior. Thus, A1/A2 asymmetric difunctionalized pillar[ 5 ]arenes can be fine-tuned through structural modification and choice of guest molecules, offering potential for the design of functional, stimuli-responsive systems. Declarations Funding: This work was supported by Kuwait Foundation for the Advancement of Science (KFAS) [Grant No. PN23-14SC-2096]. Additional support was provided by the Research Sector Projects Unit (RSPU) at Kuwait University [Grant Nos. GS01/01, GS01/03, and GS03/08]. Author Contribution All authors contributed equally to this work. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Acknowledgements The support received from Kuwait Foundation for the Advancement of Science (KFAS) and the facilities at the RSPU are gratefully acknowledged. References Ogoshi T, Yamagishi T, Nakamoto Y (2016) Pillar-shaped macrocyclic hosts pillar[n]arenes: New key players for supramolecular chemistry. Chem Rev 116:7937–8002 Bleus S, Dehaen W (2024) Pillararene-inspired arenes: Synthesis, properties and applications compared to the parent macrocycle. Coord Chem Rev 509:215762 Gomez B, Francisco V, Fernandez-Nieto F, Garcia-Rio L, Martin-Pastor M, Paleo MR, Sardina FJ (2014) Host–guest chemistry of a water-soluble pillar[5]arene: Evidence for an ionic-exchange recognition process and different complexation modes. Chem Eur J 20:12123–12132 Ohtani S, Kato K, Fa S, Ogoshi T (2022) Host–guest chemistry based on solid-state pillar[n]arenes. Coord Chem Rev 462:214503 Liu P, Li Z, Shi B, Liu J, Zhu H, Huang F (2018) Formation of linear side-chain polypseudorotaxane with supramolecular polymer backbone through neutral halogen bonds and pillar[5]arene-based host–guest interactions. Chem Eur J 24:4264–4267 Li Q, Zhu H, Huang F (2020) Pillararene-based supramolecular functional materials. Trends Chem 2:850–864 Strutt NL, Zhang H, Schneebeli ST, Stoddart JF (2014) Functionalizing pillar[n]arenes. Acc Chem Res 47:2631–2642 Xu X, Jerca VV, Hoogenboom R (2020) Structural diversification of pillar[n]arene macrocycles. Angew Chem Int Ed 59:6314–6316 Hu WB, Hu WJ, Zhao XL, Liu YA, Li JS, Jiang B, Wen K (2016) A1/A2-diamino-substituted pillar[5]arene-based acid–base-responsive host–guest system. J Org Chem 81:3877–3881 Al-Azemi TF, Mohamod AA, Vinodh M, Alipour FH (2018) A new approach for the synthesis of mono- and A1/A2-dihydroxy-substituted pillar[5]arenes and their complexation with alkyl alcohols in solution and in the solid state. Org Chem Front 5:10–18 Vinodh M, Alipour FH, Al-Azemi TF (2023) Spatially designed supramolecular anion receptors based on pillar[5]arene scaffolds: Synthesis and halide anion binding properties. ACS Omega 8:1466–1475 Wu L, Han C, Jing X, Yao Y (2021) Rim-differentiated pillar[5]arenes. Chin Chem Lett 32:3322–3330 Park B, Nierengarten I, Nierengarten JF (2025) Mechanochemical synthesis of pillar[5]arene-based [ c2 ] daisy chain rotaxanes ChemistryEurope 3:e202500002 Li Q, Hu K, Xu S, Ji X (2025) Construction of supramolecular polymer network elastomers based on pillar[5]arene/alkyl chain host–guest interactions. ACS Macro Lett 14:120–128 Vinodh M, Al-Azemi TF (2022) Linear supramolecular polymer driven by Br⋅⋅⋅Br and Br⋅⋅⋅H non-bonding interactions based on inclusion-complex of octabromo-functionalized pillar[a]arene. J Chem Cryst 52:399–406 Han Y, Xu LM, Nie CY, Jiang S, Sun J, Yan CG (2018) Synthesis of diamido-bridged bis-pillar[5]arenes and tris-pillar[5]arenes for construction of unique [1]rotaxanes and bis-[1]rotaxanes Beilstein. J Org Chem 14:1660–1667 Zhang R, Wang C, Long R, Chen T, Yan C, Yao Y (2019) Pillar[5]arene-based [1]rotaxane systems with redox-responsive host–guest property: Design, synthesis and the key role of. chain length Front Chem 7:508 Vinodh M, Al-Azemi TF (2024) Solvent-induced supramolecular self-assembly in a solid-state A1/A2-difunctionalized pillar[5]arene host CrystEngComm 26:5138–5143 Al-Azemi TF, Vinodh M (2022) External-stimulus-triggered conformational inversion of mechanically self-locked pseudo[1]catenane and gemini-catenanes based on A1/A2-alkyne–azide-difunctionalized pillar[5]. arenes RSC Adv 12:1797–1806 Rodin M, Helle D, Kuckling D (2024) Pillar[5]arene-based dually crosslinked supramolecular gel as a sensor for the detection of adiponitrile. Polym Chem 15:661–679 Moulin E, Carmona-Vargas CC, Giuseppone N (2023) Daisy chain architectures: From discrete molecular entities to polymer materials. Chem Soc Rev 52:7333–7358 Spackman PR, Turner MJ, McKinnon JJ, Wolff SK, Grimwood DJ, Jayatilaka D, Spackman MA (2021) CrystalExplorer: A program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals. J Appl Crystallogr 54:1006–1011 Turner MJ, McKinnon JJ, Wolff SK, Grimwood DJ, Spackman PR, Jayatilaka D, Spackman MA (2021) CrystalExplorer 21.5 University of Western Australia Scheme 1 Scheme 1 is available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files image1.png Scheme 1. Single crystals of A1/A2-asymmetric di-functionalized pillar[5]arenes grown under different solvent media. SupportinginformationJCCAlazemi20252.docx Cite Share Download PDF Status: Published Journal Publication published 19 Mar, 2026 Read the published version in Journal of Chemical Crystallography → Version 1 posted Editorial decision: Revision requested 11 Feb, 2026 Reviews received at journal 10 Feb, 2026 Reviews received at journal 03 Feb, 2026 Reviewers agreed at journal 31 Jan, 2026 Reviewers agreed at journal 29 Jan, 2026 Reviewers invited by journal 29 Jan, 2026 Editor assigned by journal 09 Dec, 2025 Submission checks completed at journal 09 Dec, 2025 First submitted to journal 07 Dec, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8298205","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":583439503,"identity":"f661d0a1-250b-405e-816d-5198b16ce5cb","order_by":0,"name":"Anshel Saldanha","email":"","orcid":"","institution":"Kuwait University","correspondingAuthor":false,"prefix":"","firstName":"Anshel","middleName":"","lastName":"Saldanha","suffix":""},{"id":583439504,"identity":"e7c52c0f-a36c-457c-8585-7e9ececd1ed2","order_by":1,"name":"Mickey Vinodh","email":"","orcid":"","institution":"Kuwait 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07:08:06","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8298205/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8298205/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10870-026-01090-9","type":"published","date":"2026-03-19T15:58:28+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":101639475,"identity":"251374b7-7e05-4ce1-837c-9ed96c558142","added_by":"auto","created_at":"2026-02-02 07:17:53","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":1014902,"visible":true,"origin":"","legend":"\u003cp\u003eCrystal Structure of \u003cstrong\u003eP8_D\u003c/strong\u003e and \u003cstrong\u003eP10_D\u003c/strong\u003e(Hydrogen atoms on the pillar[5]arene ring, except the propargyl hydrogen, are omitted for clarity).\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/bfd282d9569a3eff406909b0.png"},{"id":101753293,"identity":"af29f43d-aff4-4ec8-8a01-38a1dea3e098","added_by":"auto","created_at":"2026-02-03 10:39:38","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1227032,"visible":true,"origin":"","legend":"\u003cp\u003eCrystal Structure of \u003cstrong\u003eP8.ADN\u003c/strong\u003e and \u003cstrong\u003eP10.ADN\u003c/strong\u003e(Hydrogen atoms on the pillar[5]arene ring, except the propargyl hydrogen, are omitted for clarity).\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/c65606efab751c1b61d4e309.png"},{"id":101639477,"identity":"6a944b0c-da40-4a1e-8658-13b8806a102c","added_by":"auto","created_at":"2026-02-02 07:17:53","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1309678,"visible":true,"origin":"","legend":"\u003cp\u003eCrystal Structures of cyclic [\u003cem\u003ec2\u003c/em\u003e] daisy chain double threaded dimer belongs to \u003cstrong\u003eP8_D\u003c/strong\u003e and \u003cstrong\u003eP10_D\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/3fb3687f9ce1a753c8da09ae.png"},{"id":101639481,"identity":"a6542f30-c59b-45ae-bc10-8fc32a6fc32f","added_by":"auto","created_at":"2026-02-02 07:17:53","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1760355,"visible":true,"origin":"","legend":"\u003cp\u003ePossible host-guest interactions between a pillar[5]arene ring and the threaded alkyl chain belongs to its dimeric counterpart in \u003cstrong\u003eP8_D\u003c/strong\u003e and \u003cstrong\u003eP10_D\u003c/strong\u003e systems. π1–π5 are the centroids of the C1-C6, C8–C13, C15–C20, C22–C27 and C29-C34 phenyl rings respectively. Symmetry code: \u003csup\u003e(i)\u003c/sup\u003e 1.5-x, 1/2-y, 1-z (for \u003cstrong\u003eP8_D\u003c/strong\u003e) and \u003csup\u003e(i)\u003c/sup\u003e 2-x, 2-y, 2-z ( for \u003cstrong\u003eP10_D\u003c/strong\u003e).\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/9bf67874add300fafcaa9f79.png"},{"id":101880456,"identity":"138f29fb-63de-4453-9e7e-c4bcd8f0e53b","added_by":"auto","created_at":"2026-02-04 15:02:14","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":1211088,"visible":true,"origin":"","legend":"\u003cp\u003eStructures of two adjacent \u003cstrong\u003eP8.ADN\u003c/strong\u003e and \u003cstrong\u003eP10.ADN\u003c/strong\u003esystems demonstrating the mutual orientations of long alkyls among them.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/953975e820cc311456c7ce52.png"},{"id":101753075,"identity":"7320725a-3437-472c-b099-fe07c04b1d25","added_by":"auto","created_at":"2026-02-03 10:39:11","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":1256963,"visible":true,"origin":"","legend":"\u003cp\u003ePossible host-guest interactions between pillar[5]arene ring and adiponitrile guest molecule in \u003cstrong\u003eP8.ADN\u003c/strong\u003e and \u003cstrong\u003eP10.ADN\u003c/strong\u003e systems. π1–π5 are the centroids of the C1-C6, C8–C13, C15–C20, C22–C27 \u0026amp; C29-C34 phenyl rings respectively.\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/e315527a8fe092a331316886.png"},{"id":101639480,"identity":"3566a3d3-39ba-4de3-be86-cd3ea0ff7403","added_by":"auto","created_at":"2026-02-02 07:17:53","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":1531012,"visible":true,"origin":"","legend":"\u003cp\u003eChloroform based intermolecular interactions in the crystal network of \u003cstrong\u003eP8_D\u003c/strong\u003e system. (Different types of interactions are demonstrated by different colored lines as C-H⋯O- red; C-H… π - pink; Cl⋯Cl- green and C-H⋯Cl- blue). π4 is the centroid of the phenyl ring constituting C22-C27; Symmetry code: \u003csup\u003e(i)\u003c/sup\u003e 1-x, y, 1.5-z; \u003csup\u003e(ii)\u003c/sup\u003e 1.5-x, -1/2+y, 1.5-z and \u003csup\u003e(iii)\u003c/sup\u003e -1/2+x, -1/2+y.\u003c/p\u003e","description":"","filename":"image8.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/bb79e1b7f7cde896ee303195.png"},{"id":101639488,"identity":"b6046abf-061f-4a78-9536-460c8556a343","added_by":"auto","created_at":"2026-02-02 07:17:54","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":1690826,"visible":true,"origin":"","legend":"\u003cp\u003ePossible intermolecular interactions between \u003cstrong\u003eP8_D\u003c/strong\u003e dimeric systems systems in crystal network with adjacent pillar[5]arene dimers of different symmetries.\u0026nbsp; Symmetry code: \u003csup\u003e(i)\u003c/sup\u003e 1.5-x, 1/2-y, 1-z; \u003csup\u003e(ii)\u003c/sup\u003e x, 1+y, z; \u003csup\u003e(iii)\u003c/sup\u003e 1.5-x, 1.5-y, 1-z; \u003csup\u003e(iv)\u003c/sup\u003e x, -1+y, z and \u003csup\u003e(v)\u003c/sup\u003e 1.5-x,-1/2-y, 1-z; π5 is the centroid of the phenyl ring constituting C29-C34.\u003c/p\u003e","description":"","filename":"image9.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/58f5041f8156867bbed9195b.png"},{"id":101753596,"identity":"fd0bc778-5853-4cd5-98d3-bc1922c9be28","added_by":"auto","created_at":"2026-02-03 10:40:18","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":1058047,"visible":true,"origin":"","legend":"\u003cp\u003eIntermolecular interactions among \u003cstrong\u003eP8.ADN \u003c/strong\u003esystems in crystal network with adjacent pillar[5]arene molecules of different symmetries. (A) interactions showing propargyloxy and octyloxy groups (B) two sets of complementary interactions via C-H...O and C-H... π modes. Symmetry code: \u003csup\u003e(i)\u003c/sup\u003e x, 1+y, z; \u003csup\u003e(ii)\u003c/sup\u003e 1+x, y, z; \u003csup\u003e(iii)\u003c/sup\u003e x, -1+y, z; \u003csup\u003e(iv)\u003c/sup\u003e -1+x, y, z; \u003csup\u003e(v) \u003c/sup\u003e1-x, 1-y, 1-z an d \u003csup\u003e(vi) \u003c/sup\u003e2-x, 1-y, 1-z; π1 is the centroid of C37≡C38 and π2 is the centroids of the phenyl ring constituting C15-C20..\u003c/p\u003e","description":"","filename":"image10.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/12a423144784b4c1951b9fc7.png"},{"id":101639478,"identity":"762a03b0-a53e-4018-9855-70b18763dbd3","added_by":"auto","created_at":"2026-02-02 07:17:53","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":1396404,"visible":true,"origin":"","legend":"\u003cp\u003eIntermolecular interactions among\u003cstrong\u003e P10.ADN\u003c/strong\u003e systems in crystal network with adjacent pillar[5]arene molecules of different symmetries. Symmetry code: \u003csup\u003e(i)\u003c/sup\u003e 1+x, -1+y, z; \u003csup\u003e(ii)\u003c/sup\u003e x, -1+y, z; \u003csup\u003e(iii)\u003c/sup\u003e -1+x, y, z; \u003csup\u003e(iv)\u003c/sup\u003e -1+x, 1+y, z; \u003csup\u003e(v)\u003c/sup\u003e x, 1+y, z and \u003csup\u003e(vi)\u003c/sup\u003e 1+x, y, z; π1, π3, π4 \u0026amp; π5 are the centroids of the phenyl rings C1-C6, C15-C20, C22-C26 \u0026amp; C29-C34 respectively.\u003c/p\u003e","description":"","filename":"image11.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/21ba8c05a488d6803be65427.png"},{"id":101639485,"identity":"c5513018-81b2-4197-829b-3912d6685cbf","added_by":"auto","created_at":"2026-02-02 07:17:53","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":1196854,"visible":true,"origin":"","legend":"\u003cp\u003eHirshfeld surfaces (mapped with dnorm) of the \u003cstrong\u003eP8_D\u003c/strong\u003eand \u003cstrong\u003eP10_D\u003c/strong\u003e crystals.\u003c/p\u003e","description":"","filename":"image12.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/2f110df812d56a26b37fbe44.png"},{"id":105223565,"identity":"ed7a7842-5061-43f3-bb3e-4f70545f18e1","added_by":"auto","created_at":"2026-03-23 16:08:32","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":16957051,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/16633646-2ffc-49f6-9ea9-b4306c05a71b.pdf"},{"id":101880889,"identity":"aa7d6698-048c-4491-b762-5ea7af3a4a3e","added_by":"auto","created_at":"2026-02-04 15:07:26","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":961715,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1.\u003c/strong\u003e Single crystals of A1/A2-asymmetric di-functionalized pillar[5]arenes grown under different solvent media.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/c68e67e8248f47e85932cfa4.png"},{"id":101754000,"identity":"409db03c-51a7-4e1e-be97-bb4fe5219ce4","added_by":"auto","created_at":"2026-02-03 10:41:19","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":7405209,"visible":true,"origin":"","legend":"","description":"","filename":"SupportinginformationJCCAlazemi20252.docx","url":"https://assets-eu.researchsquare.com/files/rs-8298205/v1/253498748b31822589301000.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Single-Crystal X-ray Diffraction Study of [c2] Daisy Chains and Inclusion Complexes from A1/A2-Functionalized Pillar[5]arenes with Variable Chain Lengths","fulltext":[{"header":"Introduction","content":"\u003cp\u003ePillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene-based macrocycles have attained significant attention owing to their highly symmetrical, rigid architectures and electron-rich cavities, which render them excellent candidates for molecular recognition and host\u0026ndash;guest interactions [\u003cspan additionalcitationids=\"CR2 CR3 CR4\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. Functionalization of pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes, particularly at the macrocyclic rims, greatly enhances their structural and chemical versatility, enabling fine-tuning of their physicochemical properties, solubility, and binding affinities [\u003cspan additionalcitationids=\"CR7 CR8 CR9 CR10 CR11\" citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. The nature and position of substituent groups at the rim play a decisive role in governing the self-assembly behavior and supramolecular characteristics of these systems. In particular, variations in the length and flexibility of alkyl chains attached to the rims can markedly influence intermolecular interactions, molecular packing, and the resulting solid-state organization [\u003cspan additionalcitationids=\"CR14 CR15 CR16\" citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e].\u003c/p\u003e \u003cp\u003ePreviously, we reported the crystal structures of supramolecular assemblies comprising cyclic [\u003cem\u003ec2\u003c/em\u003e] daisy chain (\u0026ldquo;double-threaded dimer\u0026rdquo;) and host-guest inclusion complexes derived from an A1/A2-10-bromodecyloxy-propargyloxy-difunctionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. The influence of crystallization solvents on the solid-state supramolecular organization of this macrocycle was elucidated in detail, revealing that both [\u003cem\u003ec2\u003c/em\u003e] daisy chain rotaxanes and host\u0026ndash;guest inclusion complexes exhibit distinct packing motifs depending on the solvent system employed. To extend our previous investigations, we report a comparative crystallographic study of two A1/A2-asymmetric di-functionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes, in which one macrocyclic rim bears either n-decyloxy and propargyloxy or n-octyloxy and propargyloxy substituents which are crystallized under different solvent conditions (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) .This study aims to investigate the influence of the alkyl chain length on the self-assembly and supramolecular organization in the crystalline phase. The results provide valuable insights into the structure\u0026ndash;property relationships governing the formation of functionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene-based supramolecular architectures and contribute to the rational design of new crystalline materials with tailored supramolecular features.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Experimental","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis and crystal growth\u003c/h2\u003e \u003cp\u003e \u003cem\u003eSynthesis of 1-propargyloxy-4-octyloxy benzene\u003c/em\u003e:: 1- propargyloxy-4-hydroxy benzene [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] (1.48 g, 10 mmol) and dry potassium carbonate (2.76 g; 20 mmol ) was dissolved in dry DMF (30 ml) and 1-bromooctane (2.70 g, 14 mmol) was added. This mixture was heated at 80 \u003csup\u003eo\u003c/sup\u003eC overnight and then water (200 mL) was added to the reaction mixture. The organic fraction was then recovered by extraction with dichloromethane (200 ml). The dichloromethane fraction was washed with water (100 mL each; 5 times) to remove any DMF solvent present and then dried over Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e and did column purification using dichloromethane/hexane mixture (50:50 v/v). Yield 2.1 g (81%). \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e, δ): 0.92 (m, 3H), 1.33 (m, 8H), 1.48 (m, 2H), 1.78 (m, 2H), 2.52 (m, 1H), 3.92 (m, 2H), 4.66 (m, 2H), 6.86 (m, 2H), 6.93 (m, 2H). EI-MS: 260.06 [M].\u003c/p\u003e \u003cp\u003e \u003cem\u003eSynthesis of 1-propargyloxy-4-decyloxy benzene\u003c/em\u003e: 1- propargyloxy-4-hydroxy benzene [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e] (1.48 g, 10 mmol) and dry potassium car-bonate (2.76 g; 20 mmol ) was dissolved in dry DMF ( 30 ml) and 1-bromodecane (3.09 g, 14 mmol) was added and the reaction was proceeded similar to that of the synthesis of 1-propargyloxy-4-octyloxy benzene. Yield 2.4 g (83%). \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e, δ): 0.92 (m, 3H), 1.43 (m, 12H), 1.58 (m, 2H), 1.78 (m, 2H), 2.58 (m, 1H), 3.94 (m, 2H), 4.67 (m, 2H), 6.85 (m, 2H), 6.94 (m, 2H). EI-MS: 288.11 [M].\u003c/p\u003e \u003cp\u003e \u003cem\u003eSynthesis of 1-(1-propargyloxy-4-octyloxy)-2,3,4,5- dimethoxy pillar\u003c/em\u003e[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]\u003cem\u003earene (\u003c/em\u003e\u003cb\u003eP8\u003c/b\u003e\u003cem\u003e)\u003c/em\u003e: Paraformaldehyde (3.1 g, 100 mmol) was added to a solution of 1,4-dimethoxybenzene (4.4 g, 32 mmol) and 1-propargyloxy-4-octyloxy benzene (520 mg, 2 mmol) in dichloromethane (250 mL) under nitrogen atmosphere. Boron trifluoride diethyl etherate (4 ml, 32 mmol) was then added to the solution and the mixture was stirred at 0 \u003csup\u003eo\u003c/sup\u003eC for 1 h. Methanol (400 mL) was poured into the mixture to quench the reaction and filtered. The residue was dissolved in chloroform (100 mL) and filtered. The filtrate was concentrated to a small volume and adsorbed on silica and did column using dichloromethane : hexane mixture (60:40 v/v). The second last fraction was the intended pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene. Yield: 387 mg (22%). \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e, δ): 0.81 (m, 3H), 1.12 (m, 4H), 1.28 (m, 2H), 1.34 (m, 2H), 1.51 (m, 2H), 1.80 (m, 2H), 1.93 (m, 1H), 3.69 (m, 24H), 3.80 (m, 8H), 3.82 (s, 2H), 3.90 (m, 2H), 4.40 (m, 2H), 6.76 (s, 1H), 6.77 (s, 1H), 6.79 (s, 1H), 6.81 (s, 1H), 6.82 (m, 4H), 6.84 (m, 2H). \u003csup\u003e13\u003c/sup\u003eC NMR (150 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e, δ): 14.2, 22.7, 26.4, 29.4, 29.4, 29.6, 29.8, 29.8, 29.9, 30.7, 31.8, 55.9, 55.9, 56.0, 56.3, 68.9, 74.9, 79.0, 114.1, 114.2, 114.2, 114.2, 114.3, 114.4, 114.6, 115.4, 115.7, 128.2, 128.4, 128.4, 128.5, 128.6, 128.7, 128.7, 128.8, 129.0, 148.9, 150.8, 150.9, 151.0, 151.0, 151.0. HRMS (EI) \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e: [M]\u003csup\u003e+\u003c/sup\u003e calcd for C\u003csub\u003e54\u003c/sub\u003eH\u003csub\u003e64\u003c/sub\u003eO\u003csub\u003e10\u003c/sub\u003e, 872.4494; found, 872.4495.\u003c/p\u003e \u003cp\u003e \u003cem\u003eSynthesis of 1-(1-propargyloxy-4-decyloxy)-2,3,4,5- dimethoxy pillar\u003c/em\u003e[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]\u003cem\u003earene (\u003c/em\u003e\u003cb\u003eP10\u003c/b\u003e\u003cem\u003e)\u003c/em\u003e: Paraformaldehyde (3.1 g, 100 mmol) was added to a solution of 1,4-dimethoxybenzene (4.4 g, 32 mmol) and 1-propargyloxy-4-decyloxy benzene (576 mg, 2 mmol) in dichloromethane (250 mL) under nitrogen atmosphere. Boron trifluoride diethyl etherate (4 ml, 32 mmol) was then added to the solution and the reaction and the product purification was carried out similar to those for the synthesis of \u003cb\u003eP8\u003c/b\u003e. Yield: 372 mg (21%). \u003csup\u003e1\u003c/sup\u003eH NMR (400 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e, δ): 0.82 (m, 3H), 1.12 (m, 6H), 1.28 (m, 4H), 1.35 (m, 2H), 1.52 (m, 2H), 1.80 (m, 2H), 1.87 (m, 1H), 3.68 (m, 24H), 3.79 (m, 8H), 3.83 (s, 2H), 3.92 (m, 2H), 4.42 (m, 2H), 6.74 (s, 1H), 6.76 (s, 1H), 6.78 (s, 1H), 6.81 (s, 2H), 6.81 (m, 2H), 6.82 (m, 2H), 6.83 (s, 1H). \u003csup\u003e13\u003c/sup\u003eC NMR (150 MHz, CDCl\u003csub\u003e3\u003c/sub\u003e, δ): 14.1, 22.7, 22.8, 26.3, 29.4, 29.4, 29.7, 29.8, 29.9, 29.9, 30.4, 31.8, 55.8, 55.9, 56.0, 56.3, 68.8, 74.9, 79.1, 114.1, 114.1, 114.2, 114.2, 114.3, 114.5, 114.6, 115.3, 115.7, 128.2, 128.3, 128.5, 128.6, 128.7, 128.7, 128.9, 129.0, 148.9, 150.8, 150.8, 151.0, 151.0, 151.1. HRMS (EI) \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e: [M]\u003csup\u003e+\u003c/sup\u003e calcd for C\u003csub\u003e56\u003c/sub\u003eH\u003csub\u003e68\u003c/sub\u003eO\u003csub\u003e10\u003c/sub\u003e, 900.4807; found, 900.4809.\u003c/p\u003e \u003cp\u003e \u003cem\u003eCrystal growth\u003c/em\u003e: Single crystals of these pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene systems were grown by slow evaporation of either \u003cb\u003eP8\u003c/b\u003e or \u003cb\u003eP10\u003c/b\u003e (10 mg) from 1.0 mL of chloroform/cyclohexane (8:2 v/v) or chloro-form/adiponitrile (8:2 v/v) solvent mixtures. The resulting crystals were analyzed via single-crystal X-ray diffraction.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eInstrumentation and crystal refinement\u003c/h3\u003e\n\u003cp\u003eNuclear magnetic resonance (NMR) spectroscopy was done either by Bruker Avance II 600 MHz (Germany) or by Burker DPX 400 MHz spectrometers. Electron impact ionization (EI) mass spectrometry was performed using Thermo Scientific DFS High Resolution GC/MS (Germany) mass spectrometer.\u003c/p\u003e \u003cp\u003eThe single crystal data collection were made on Rigaku Rapid II (Japan) diffractometer by Mo-Kα radiation. The crystal data collected were processed by \u0026lsquo;Crystalclear\u0026rsquo; software package. The structures were then solved by direct methods using \u0026lsquo;CrystalStructure\u0026rsquo; crystallographic software package and the refinement were performed using SHELXL-2019/3. All non-hydrogen atoms were refined anisotropically and hydrogen atoms were refined using the riding model.\u003c/p\u003e \u003cp\u003eIn the \u003cb\u003eP8_D\u003c/b\u003e crystal, the SIMU and DELU commands were used to restrain the thermal displacement parameters of the n-octyloxy chain of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene, while DFIX and DANG were applied to adjust its geometry. The geometry of the propargyloxy substituent also adjusted by DFIX command. One of the solvent chloroform molecules in this crystal is disordered a special position and is refined by part \u0026minus;\u0026thinsp;1 command. The hydrogen atom in this diordered molecule is assaigned from the electron density map. SIMU and DELU were used to restrain thermal displacement parameters, while DFIX, DANG were employed to refine the geometry of the all chloroform molecules in this crystal. In the \u003cb\u003eP10_D\u003c/b\u003e crystal, the SIMU and DELU commands were used to restrain the thermal displacement parameters of the n- decyloxy chain of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene, while DFIX and DANG were used to adjust its geometry. In addition, DFIX, DANG were employed to refine the geometry of the cyclohexane molecule present in this crystal and SIMU and DELU were used to restrain thermal displacement parameters of these solvent atoms.\u003c/p\u003e \u003cp\u003eIn the \u003cb\u003eP8\u0026middot;ADN\u003c/b\u003e crystal, DFIX and DANG were applied to refine the molecular geometry, and the SIMU and DELU commands were used to restrain the thermal displacement parameters of the n-octyloxy chain and the propargyloxy fragment of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene. Furthermore, for the encapsulated adiponitrile molecule, SIMU and DELU were employed to restrain its thermal displacement parameters, while DFIX and DANG were applied to refine its geometry. In the \u003cb\u003eP10\u0026middot;ADN\u003c/b\u003e crystal, the SIMU and DELU commands were applied to restrain the thermal displacement parameters, while DFIX and DANG were used to adjust the geometries of both the n- decyloxy chain of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene and the adiponitrile guest molecule.\u003c/p\u003e \u003cp\u003eThe crystallographic data for the structures reported in this paper has been deposited at the Cambridge Crystallographic Data Centre (CCDC 2497292\u0026ndash;2497295).\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eCrystal structures of A1/A2-difunctionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes\u003c/h2\u003e \u003cp\u003ePillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene macrocycles possess a strong tendency to encapsulate linear molecules within their electron-rich cavities. When a long, linear alkyl chain is introduced at the rim of the macrocycle, it can undergo self-inclusion into its own cavity or inter-inclusion into the cavity of a neighboring macrocycle. In contrast, the presence of a competing guest molecule prevents this intramolecular threading, causing the alkyl chain to project outward from the already occupied cavity.\u003c/p\u003e \u003cp\u003eIn our previous work, we reported the crystal structures and supramolecular self-assembly of an A1/A2-10-bromodecyloxy-propargyloxy-difunctionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene under various crystallization conditions [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. When crystallized from chloroform or N,N-dimethylformamide (DMF), the system yielded cyclic [\u003cem\u003ec2\u003c/em\u003e] daisy chain \u0026ldquo;double-threaded dimer\u0026rdquo; assemblies. Alternatively, crystallization from a chloroform solution containing adiponitrile produced host\u0026ndash;guest inclusion complexes. Adiponitrile, a well-established guest for pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes, is particularly effective due to its strong encapsulation ability [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Moreover, both the [\u003cem\u003ec2\u003c/em\u003e] daisy chain rotaxanes and the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene\u0026ndash;adiponitrile inclusion complexes displayed distinct supramolecular packing arrangements in the crystalline state depending on the solvent employed, underscoring the critical influence of solvent environment on the solid-state assembly of functionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes.\u003c/p\u003e \u003cp\u003eThe influence of long alkyl chain in the formation of such pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene-adiponitrile host-guest systems or double-threaded dimer and their consequent propagation into supramolecular self-assembly requires detailed investigation. So, in this present work we designed two pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene derivatives to explore this effect: one featuring n-decyloxy-propargyloxy groups (\u003cb\u003eP10\u003c/b\u003e) and the other with n-octyloxy-propargyloxy groups (\u003cb\u003eP8\u003c/b\u003e), both functionalized at the A1/A2 positions. This design allows us to systematically study how variations in alkyl chain length influence the supramolecular behavior of these systems.\u003c/p\u003e \u003cp\u003eThe synthesis and characterization of \u003cb\u003eP8\u003c/b\u003e and \u003cb\u003eP10\u003c/b\u003e are detailed in the Experimental Section. Single crystals of each compound were grown using two different solvent systems: chloroform/cyclohexane (8:2 v/v) and chloroform/adiponitrile (8:2 v/v). The resulting crystals were analyzed via single crystal X-ray diffraction. The crystal structures obtained from chloroform/cyclohexane (denoted as \u003cb\u003eP8_D\u003c/b\u003e and \u003cb\u003eP10_D\u003c/b\u003e) and those from chloroform/adiponitrile (denoted as \u003cb\u003eP8.ADN\u003c/b\u003e and \u003cb\u003eP10.ADN\u003c/b\u003e) are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Their corresponding crystallographic data are summarized in Supporting information (\u003cb\u003eTables S1-S2\u003c/b\u003e). Thermal ellipsoid representations of the asymmetric units for all four crystal structures are also provided in the Supporting Information (\u003cb\u003eFig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e-S4\u003c/b\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe asymmetric unit of \u003cb\u003eP8_D\u003c/b\u003e comprises one pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene molecule and one and a half co-crystallized chloroform molecules. In contrast, the asymmetric unit of \u003cb\u003eP10_D\u003c/b\u003e, crystallized from the same chloroform-cyclohexane solvent mixture, contains one pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene molecule along with one co-crystallized cyclohexane molecule. Notably, in both \u003cb\u003eP8_D\u003c/b\u003e and \u003cb\u003eP10_D\u003c/b\u003e, the n-octyl and n-decyl chains of adjacent pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene molecules are double-threaded into each other's cavities, giving rise to a cyclic [\u003cem\u003ec2\u003c/em\u003e] daisy chain-type supramolecular dimer. These [\u003cem\u003ec2\u003c/em\u003e] daisy chain structures- also referred to as double threaded dimers- are formed by two interpenetrated, half-note-shaped components and represent the simplest form of mechanically interlocked macrocyclic systems. Such assemblies can reversibly switch between threaded and unthreaded (open) states, making them valuable in biomimetic research and the design of artificial molecular machines and supramolecular polymers [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. Similarly, the reversible formation of pseudo[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]rotaxane and/or double-threaded dimer can be controlled via competing guest molecules in the supramolecular systems. The formation of these dimers in both \u003cb\u003eP8_D\u003c/b\u003e and \u003cb\u003eP10_D\u003c/b\u003e is primarily driven by multiple C\u0026ndash;H⋯O and C\u0026ndash;H⋯π interactions involving the threaded alkyl chains within the macrocyclic cavities. In \u003cb\u003eP8_D\u003c/b\u003e, the dimer formation is further stabilized by interaction through the co-crystallized chloroform molecules, which act as caps at both ends of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene cavity via C\u0026ndash;H⋯Cl contacts, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. Detailed quantitative data on the non-covalent interactions- including interaction distances and angles- are provided in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. In the case of \u003cb\u003eP10_D\u003c/b\u003e, however, the n-decyl chains are confined within the host cavity solely through C\u0026ndash;H⋯O and C\u0026ndash;H⋯π interactions, without any additional stabilization from co-crystallized solvent molecules. This behavior is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e and the quantitative data are provided in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eNon-bonding interactions between pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene cavity and octyloxy chain in \u003cb\u003eP8_D\u003c/b\u003e daisy chain double-threaded dimer ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC39\u003csup\u003ei\u003c/sup\u003e-H39B\u003csup\u003ei\u003c/sup\u003e ⋯O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.079\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.88(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e141.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC40-H40A⋯O4\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.882\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.68(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e140.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC41-H41A⋯O10\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.391\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.32(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e161.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC41-H41B⋯O8\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.076\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.94(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e148.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC42-H42A⋯π1\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.937\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.900\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e172.33\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC42-H42B⋯ π2\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.872\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.635\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e136.30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC43-H43A⋯ π5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.023\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.972\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e166.23\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC43-H43B⋯ π4\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.999\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.760\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e127.50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC44-H44A⋯O1\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.378\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.23(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e147.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC44-H44B⋯O3\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.124\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.07(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e165.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC45-H45A⋯O7\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.011\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.64(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e123.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC45-H45B⋯O5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.178\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.06(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e152.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC46-H46C⋯Cl4\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.833\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.65(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e144\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eSymmetry code: \u003csup\u003e(i)\u003c/sup\u003e 1.5-x, 1/2-y, 1-z; π1, π2, π4 \u0026amp; π5 are the centroids of the phenyl rings C1-C6, C8-C13, C22-C27 \u0026amp; C29-C34 respectively.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eNon-bonding interactions between pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene cavity and decayloxy chain in \u003cb\u003eP10_D\u003c/b\u003e daisy chain double-threaded dimer ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC39\u003csup\u003ei\u003c/sup\u003e-H39B\u003csup\u003ei\u003c/sup\u003e ⋯O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.097\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.88(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e138.9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC40-H40A⋯O4\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.917\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.74(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e143.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC41-H41B⋯O8\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.135\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.10(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e176.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC42-H42A⋯π1\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.066\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.922\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e147.90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC42-H42B⋯ π3\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.224\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.057\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e145.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC43-H43A⋯ π4\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.864\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.762\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e154.39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC43-H43B⋯ π5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.974\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.911\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e162.60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC44-H44A⋯O1\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.291\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.26(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e173.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC44-H44B⋯O3\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.219\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.97(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e135.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC45-H45B⋯O7\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.351\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.88(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e116.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eSymmetry code: \u003csup\u003e(i)\u003c/sup\u003e 2-x, 2-y, 2-z; π1, π3, π4 \u0026amp; π5 are the centroids of the phenyl rings C1-C6, C15-C20, C22-C27 \u0026amp; C29-C34 respectively.\u003c/p\u003e \u003cp\u003eThe crystal structures of \u003cb\u003eP8.ADN\u003c/b\u003e and \u003cb\u003eP10.ADN\u003c/b\u003e, in which the respective pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes were crystallized from a chloroform\u0026ndash;adiponitrile solvent system, show that the adiponitrile (\u003cb\u003eADN\u003c/b\u003e) molecule is encapsulated within the cavities of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes, forming host\u0026ndash;guest inclusion complexes. Notably, no additional solvent molecules are co-crystallized within the lattice as space-filling agents. Although both pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene systems form inclusion complexes with adiponitrile, their solid-state structural features differ slightly. In the \u003cb\u003eP8.ADN\u003c/b\u003e crystal, the propargyloxy functional group is oriented inward toward the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene cavity, while the n-octyloxy chain extends outward from the macrocycle. In contrast, the \u003cb\u003eP10.ADN\u003c/b\u003e crystal exhibits the opposite arrangement: the propargyloxy group points outward, and the n-decyloxy chain bends inward toward the macrocycle. This difference in orientation becomes especially apparent when comparing two adjacent pillararene molecules in each crystal, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. Such structural deviations significantly influence the supramolecular self-assembly within the crystal network - a topic discussed in detail in the following section. In both \u003cb\u003eP8.ADN\u003c/b\u003e and \u003cb\u003eP10.ADN\u003c/b\u003e systems, the adiponitrile guest is stabilized by multiple C\u0026ndash;H⋯O and C\u0026ndash;H⋯π interactions, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e and summarized in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eHost-guest interactions between Pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene host and adiponitrile guest in \u003cb\u003eP8.ADN\u003c/b\u003e crystals ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC38-H38 ⋯N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.93\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.73\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e2.93(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e93.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC56-H56A⋯O5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.102\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.99(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e153.4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC56-H56B⋯O7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.049\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.85(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e141.3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC57-H57A⋯π1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.002\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.786\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e138.76\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC57-H57B⋯ π2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.620\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.760\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e163.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC58-H58A⋯ π4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.081\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.940\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e148.33\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC58-H58B⋯ π3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.241\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.055\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e142.69\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC59-H59A⋯O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.169\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.98(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e142.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC59-H59B⋯ π2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.107\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.871\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e136.83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eπ1-π 4 are the centroids of the phenyl rings C1-C6, C8-C13, C15-C20 \u0026amp; C22-C27 respectively.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eHost-guest interactions between Pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene host and adiponitrile guest in \u003cb\u003eP10.ADN\u003c/b\u003e crystals ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC51-H51A ⋯N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.960\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.997\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.87(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e153.26\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC58-H58A⋯O9\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.888\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.81(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e159\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC58-H58B⋯O7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.003\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.77(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e136\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC59-H59A⋯π2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.210\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.740\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e116.12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC59-H59B⋯ π3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.152\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.051\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e154.72\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC60-H60A⋯ π5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.124\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.750\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e123.63\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC60-H60B⋯ π4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.916\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.858\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e164.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC61-H61A⋯O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.026\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.91(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e152.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC61-H61B⋯ π3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.968\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.879\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e156.82\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC54-H54A⋯N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.960\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.081\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.84(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e137.30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eπ2-π5 are the centroids of the phenyl rings C8-C13, C15-C20, C22-C27 \u0026amp; C29-C34 respectively.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eIntermolecular non-bonding interactions\u003c/h3\u003e\n\u003cp\u003eThe pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene-based double-threaded dimers and 1:1 inclusion complexes studied here exhibit a variety of non-covalent interactions within their crystal networks. These non-bonding interactions - occurring at distances shorter than typical van der Waals contacts - play a crucial role in stabilizing the crystal structures. The interactions between each pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene systems and their immediate neighboring molecules are illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe intermolecular non-covalent interactions observed in the \u003cb\u003eP8_D\u003c/b\u003e crystals are particularly noteworthy. The solvent chloroform plays an active role in stabilizing the crystal structure through various interactions, including C\u0026ndash;H⋯π, C\u0026ndash;H⋯O, C\u0026ndash;H⋯Cl, and Cl⋯Cl contacts, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. Remarkably, the chloroform molecules at a given lattice position interact with four pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene molecules of different symmetries in this crystal. Beyond the chloroform-mediated interactions, each pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene unit also engages in direct contacts with two neighboring pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes via C\u0026ndash;H⋯π and C\u0026ndash;H⋯O interactions. The C\u0026ndash;H⋯π interaction originates specifically from the propargyl moiety of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe \u003cb\u003eP10_D\u003c/b\u003e crystals exhibit a nearly identical pattern of intermolecular pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene\u0026ndash;pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene interactions, involving C\u0026ndash;H⋯π (from the propargyl end) and C\u0026ndash;H⋯O contacts (Supporting information; \u003cb\u003eFig. S5\u003c/b\u003e). However, unlike \u003cb\u003eP8_D\u003c/b\u003e, the \u003cb\u003eP10_D\u003c/b\u003e crystals do not display any solvent-mediated interactions. Quantitative data on these non-covalent interactions for \u003cb\u003eP8_D\u003c/b\u003e and \u003cb\u003eP10_D\u003c/b\u003e crystals are provided in Tables\u0026nbsp;\u003cspan refid=\"Tab5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u0026amp; \u003cspan refid=\"Tab6\" class=\"InternalRef\"\u003e6\u003c/span\u003e respectively.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab5\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 5\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eIntermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the \u003cb\u003eP8_D\u003c/b\u003e crystals ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC47-H47B⋯O10\u003csup\u003eiv\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.654\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.611(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e172.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC38-H38⋯π5\u003csup\u003eiv\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.93\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.237\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.003\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e140.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC46\u003csup\u003eiii\u003c/sup\u003e-H46C\u003csup\u003eiii\u003c/sup\u003e⋯Cl4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.833\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.65(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e144\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC55-H55⋯ π4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.98\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.323\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.298\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e173.75\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC56-H56⋯O5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.404\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.233\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e145\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC56-Cl5⋯Cl3\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e1. 75(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.23(1)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.84(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e152.3(8)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eSymmetry code: \u003csup\u003e(i)\u003c/sup\u003e 1-x, y, 1.5-z; \u003csup\u003e(iii)\u003c/sup\u003e -1/2\u0026thinsp;+\u0026thinsp;x, -1/2\u0026thinsp;+\u0026thinsp;y. \u003csup\u003e(iv)\u003c/sup\u003e x, -1\u0026thinsp;+\u0026thinsp;y, z; π 4 and π 5 are the centroid of the phenyl rings constituting C22-C27 and C29-C34 respectively.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab6\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 6\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eIntermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the \u003cb\u003eP10_D\u003c/b\u003e crystals ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC38-H38⋯ π5\u003csup\u003eiv\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.93\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.451\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.264\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e147.41\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC49-H49A⋯O10\u003csup\u003eiv\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.714\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.607(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e155.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eSymmetry code: \u003csup\u003e(iv)\u003c/sup\u003e x, 1\u0026thinsp;+\u0026thinsp;y, z; π5 is the centroid of the phenyl ring constituting C29-C34.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn the \u003cb\u003eP8.ADN\u003c/b\u003e crystal, each pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene macrocycle interacts with six neighboring pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene molecules of different symmetries within the crystal lattice. Both the propargyloxy and n-octyloxy groups participate in these intermolecular interactions, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e. Notably, two distinct types of complementary non-covalent interactions are observed in the crystal network: C\u0026ndash;H⋯O and C\u0026ndash;H⋯π interactions, depicted too in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e. The quantitative details of these interactions are provided in Table\u0026nbsp;\u003cspan refid=\"Tab7\" class=\"InternalRef\"\u003e7\u003c/span\u003e. Similarly, in the \u003cb\u003eP10.ADN\u003c/b\u003e crystal, each pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene macrocycle also engages with six other pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene units of varying symmetry via C\u0026ndash;H⋯π interactions, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e and detailed in Table\u0026nbsp;\u003cspan refid=\"Tab8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. However, unlike \u003cb\u003eP8.ADN\u003c/b\u003e, the propargyloxy group in \u003cb\u003eP10.ADN\u003c/b\u003e does not participate in any significant intermolecular interactions. Therefore, \u003cb\u003eP10.ADN\u003c/b\u003e is the only system in this study where the propargyloxy terminal group of the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene does not contribute meaningfully to the crystal's non-covalent contacts.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab7\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 7\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eIntermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the \u003cb\u003eP8.ADN\u003c/b\u003e crystals ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC46-H46A⋯O10\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.647\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.58(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e165.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC49-H49B⋯ π2\u003csup\u003ev\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.953\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.848\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e155.60\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC50-H50B⋯O8\u003csup\u003evi\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.711\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.655(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e167.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC54-H54B⋯ π1\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.961\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.701\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e134.83\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eSymmetry code: \u003csup\u003e(i)\u003c/sup\u003e x, 1\u0026thinsp;+\u0026thinsp;y, z; \u003csup\u003e(ii)\u003c/sup\u003e 1\u0026thinsp;+\u0026thinsp;x, y, z; \u003csup\u003e(v)\u003c/sup\u003e 1-x, 1-y, 1-z; \u003csup\u003e(vi)\u003c/sup\u003e 2-x, 1-y, 1-z; π1 is the centroid of C37\u0026thinsp;\u0026equiv;\u0026thinsp;C38 and π2 is the centroids of the phenyl ring constituting C15-C20.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab8\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 8\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eIntermolecular non-bonding interactions (shorter than the sum of van der Walls radii) in the \u003cb\u003eP10.ADN\u003c/b\u003e crystals ( \u0026Aring;, \u003csup\u003eo\u003c/sup\u003e).\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"10\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eA-B\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eB...C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c8\" namest=\"c7\"\u003e \u003cp\u003eA....C\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c10\" namest=\"c9\"\u003e \u003cp\u003eA-B...C\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC36-H36A⋯ π3\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.304\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.101\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e140.82\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC39-H39A⋯ π4\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.360\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.059\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e130.71\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC46-H46B⋯ π5\u003csup\u003eiii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.97\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e2.915\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e3.748\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e144.56\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC53-H53C⋯ π1\u003csup\u003ev\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003e0.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e \u003cp\u003e3.305\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e \u003cp\u003e4.159\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"2\" nameend=\"c9\" namest=\"c8\"\u003e \u003cp\u003e149.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colspan=\"1\" nameend=\"c10\" namest=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eSymmetry code: \u003csup\u003e(i)\u003c/sup\u003e 1\u0026thinsp;+\u0026thinsp;x, -1\u0026thinsp;+\u0026thinsp;y, z; \u003csup\u003e(ii)\u003c/sup\u003e x, -1\u0026thinsp;+\u0026thinsp;y, z; \u003csup\u003e(iii)\u003c/sup\u003e -1\u0026thinsp;+\u0026thinsp;x, y, z; \u003csup\u003e(v)\u003c/sup\u003e x, 1\u0026thinsp;+\u0026thinsp;y, z; π1, π3, π4 \u0026amp; π5 are the centroids of the phenyl rings C1-C6,C15-C20, C22-C26 \u0026amp; C29-C34 respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe packing pattern of the \u003cb\u003eP8.ADN\u003c/b\u003e complex reveals that the crystal network organizes into one-dimensional channels along the a-axis. Similarly, the \u003cb\u003eP10.ADN\u003c/b\u003e complex also forms one-dimensional channels in the same direction, with only minor deviations in its packing features compared to \u003cb\u003eP8.ADN\u003c/b\u003e. For the \u003cb\u003eP8_D\u003c/b\u003e and \u003cb\u003eP10_D\u003c/b\u003e dimeric systems, the packing patterns exhibit a comparable propagation of dimeric pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene units, with the resulting channels being occupied by solvent molecules. Detailed packing features for all four pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene systems studied in this work are provided in the Supporting Information (\u003cb\u003eFig. S7\u003c/b\u003e \u0026amp; \u003cb\u003eFig. S8\u003c/b\u003e).\u003c/p\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eHirshfeld surface analysis structures\u003c/h2\u003e \u003cp\u003eThe non-covalent interactions present in the [\u003cem\u003ec2\u003c/em\u003e] daisy chain rotaxanes and the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene\u0026ndash;adiponitrile host\u0026ndash;guest inclusion complexes discussed in this study were further analyzed using Hirshfeld surface (HS) analysis [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. The intermolecular interactions in the \u003cb\u003eP8_D\u003c/b\u003e and \u003cb\u003eP10_D\u003c/b\u003e crystals visualized through the 3D dnorm surface obtained from Hirshfeld surface analysis is given in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e. In both crystals, the red and white regions located at the center of the macrocyclic cavities represent contacts shorter than the sum of the van der Waals radii, corresponding mainly to C\u0026ndash;H⋯O and C\u0026ndash;H⋯π interactions involved in the formation of the threaded dimers. Additionally, in \u003cb\u003eP8_D\u003c/b\u003e, non-covalent interactions involving chloroform molecules are clearly visualized as in-tense red spots on the surface. Other pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene-pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene connection contacts are also seen in the systems as red spots and/or white regions. Hirshfeld surface analysis of \u003cb\u003eP8.ADN\u003c/b\u003e and \u003cb\u003eP10.ADN\u003c/b\u003e indicated host-guest non-bonding interactions between pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene host and adiponitrile guest as white coloured regions inside the macrocyclic cavities (Supporting information; \u003cb\u003eFig. S6\u003c/b\u003e). Strong intermolecular interactions between adjacent pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene units were also evident from the 3D dnorm of HS surfaces. To quantitatively summarize these interactions, 2D fingerprint plots were gen-erated from the HS data. From the 2D fingerprint plots, the major intermolecular interactions in the \u003cb\u003eP8_D\u003c/b\u003e crystal are H⋯H (60.5%), C...H (21.6), O⋯H (7.0%), Cl⋯H (8.1%) and C\u0026hellip;C (1.2%) where as for \u003cb\u003eP10_D\u003c/b\u003e they are H⋯H (71.5%), C...H (20.7), O⋯H (6.4%) and C\u0026hellip;C (1.3%). In the case of inclusion complexes the corresponding values are H⋯H (66.4%), C...H (20.9), O⋯H (6.6%), N⋯H (4.9%) and C\u0026hellip;C (0.8%) (for \u003cb\u003eP8.ADN\u003c/b\u003e) and H⋯H (66.5%), C...H (21.2), O⋯H (6.4%), N⋯H (4.7%) and C\u0026hellip;C (1.2%) (for \u003cb\u003eP10.ADN\u003c/b\u003e) respectively. These fingerprint plots provide valuable quantitative insight into the dominant types of intermolecular interactions present in each crystal structure\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe synthesis and characterization of A1/A2 asymmetric difunctionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes, bearing propargyloxy groups at one rim and either n-decyloxy or n-octyloxy groups at the other, were accomplished. Depending on the crystallization conditions, these macrocycles formed distinct supramolecular crystal architectures. In the absence of strong encapsulating ligands, pair of pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes assembled into cyclic [\u003cem\u003ec2\u003c/em\u003e] daisy-chain type \u0026ldquo;double-threaded dimers\u0026rdquo; formed in which the long alkyl chains threaded through each other\u0026rsquo;s cavity. When adiponitrile molecules were present in the crystallization solvent, host\u0026ndash;guest inclusion complexes between the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes and adiponitrile gave rise to extended crystal networks. The resulting supramolecular assemblies were thoroughly characterized by single-crystal X-ray diffraction and Hirshfeld surface analysis. Results revealed that the alkyl chain length on the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene skeleton influenced the structural features, noncovalent interactions, and self-assembly behavior. Thus, A1/A2 asymmetric difunctionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes can be fine-tuned through structural modification and choice of guest molecules, offering potential for the design of functional, stimuli-responsive systems.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eFunding:\u003c/h2\u003e \u003cp\u003eThis work was supported by Kuwait Foundation for the Advancement of Science (KFAS) [Grant No. PN23-14SC-2096]. Additional support was provided by the Research Sector Projects Unit (RSPU) at Kuwait University [Grant Nos. GS01/01, GS01/03, and GS03/08].\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eAll authors contributed equally to this work. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThe support received from Kuwait Foundation for the Advancement of Science (KFAS) and the facilities at the RSPU are gratefully acknowledged.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eOgoshi T, Yamagishi T, Nakamoto Y (2016) Pillar-shaped macrocyclic hosts pillar[n]arenes: New key players for supramolecular chemistry. Chem Rev 116:7937\u0026ndash;8002\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBleus S, Dehaen W (2024) Pillararene-inspired arenes: Synthesis, properties and applications compared to the parent macrocycle. Coord Chem Rev 509:215762\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGomez B, Francisco V, Fernandez-Nieto F, Garcia-Rio L, Martin-Pastor M, Paleo MR, Sardina FJ (2014) Host\u0026ndash;guest chemistry of a water-soluble pillar[5]arene: Evidence for an ionic-exchange recognition process and different complexation modes. Chem Eur J 20:12123\u0026ndash;12132\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eOhtani S, Kato K, Fa S, Ogoshi T (2022) Host\u0026ndash;guest chemistry based on solid-state pillar[n]arenes. Coord Chem Rev 462:214503\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiu P, Li Z, Shi B, Liu J, Zhu H, Huang F (2018) Formation of linear side-chain polypseudorotaxane with supramolecular polymer backbone through neutral halogen bonds and pillar[5]arene-based host\u0026ndash;guest interactions. Chem Eur J 24:4264\u0026ndash;4267\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi Q, Zhu H, Huang F (2020) Pillararene-based supramolecular functional materials. Trends Chem 2:850\u0026ndash;864\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eStrutt NL, Zhang H, Schneebeli ST, Stoddart JF (2014) Functionalizing pillar[n]arenes. Acc Chem Res 47:2631\u0026ndash;2642\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXu X, Jerca VV, Hoogenboom R (2020) Structural diversification of pillar[n]arene macrocycles. Angew Chem Int Ed 59:6314\u0026ndash;6316\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHu WB, Hu WJ, Zhao XL, Liu YA, Li JS, Jiang B, Wen K (2016) A1/A2-diamino-substituted pillar[5]arene-based acid\u0026ndash;base-responsive host\u0026ndash;guest system. J Org Chem 81:3877\u0026ndash;3881\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAl-Azemi TF, Mohamod AA, Vinodh M, Alipour FH (2018) A new approach for the synthesis of mono- and A1/A2-dihydroxy-substituted pillar[5]arenes and their complexation with alkyl alcohols in solution and in the solid state. Org Chem Front 5:10\u0026ndash;18\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVinodh M, Alipour FH, Al-Azemi TF (2023) Spatially designed supramolecular anion receptors based on pillar[5]arene scaffolds: Synthesis and halide anion binding properties. ACS Omega 8:1466\u0026ndash;1475\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWu L, Han C, Jing X, Yao Y (2021) Rim-differentiated pillar[5]arenes. Chin Chem Lett 32:3322\u0026ndash;3330\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePark B, Nierengarten I, Nierengarten JF (2025) Mechanochemical synthesis of pillar[5]arene-based [\u003cem\u003ec2\u003c/em\u003e] daisy chain rotaxanes ChemistryEurope 3:e202500002\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi Q, Hu K, Xu S, Ji X (2025) Construction of supramolecular polymer network elastomers based on pillar[5]arene/alkyl chain host\u0026ndash;guest interactions. ACS Macro Lett 14:120\u0026ndash;128\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVinodh M, Al-Azemi TF (2022) Linear supramolecular polymer driven by Br\u0026sdot;\u0026sdot;\u0026sdot;Br and Br\u0026sdot;\u0026sdot;\u0026sdot;H non-bonding interactions based on inclusion-complex of octabromo-functionalized pillar[a]arene. J Chem Cryst 52:399\u0026ndash;406\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHan Y, Xu LM, Nie CY, Jiang S, Sun J, Yan CG (2018) Synthesis of diamido-bridged bis-pillar[5]arenes and tris-pillar[5]arenes for construction of unique [1]rotaxanes and bis-[1]rotaxanes Beilstein. J Org Chem 14:1660\u0026ndash;1667\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang R, Wang C, Long R, Chen T, Yan C, Yao Y (2019) Pillar[5]arene-based [1]rotaxane systems with redox-responsive host\u0026ndash;guest property: Design, synthesis and the key role of. chain length Front Chem 7:508\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVinodh M, Al-Azemi TF (2024) Solvent-induced supramolecular self-assembly in a solid-state A1/A2-difunctionalized pillar[5]arene host CrystEngComm 26:5138\u0026ndash;5143\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAl-Azemi TF, Vinodh M (2022) External-stimulus-triggered conformational inversion of mechanically self-locked pseudo[1]catenane and gemini-catenanes based on A1/A2-alkyne\u0026ndash;azide-difunctionalized pillar[5]. arenes RSC Adv 12:1797\u0026ndash;1806\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRodin M, Helle D, Kuckling D (2024) Pillar[5]arene-based dually crosslinked supramolecular gel as a sensor for the detection of adiponitrile. Polym Chem 15:661\u0026ndash;679\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMoulin E, Carmona-Vargas CC, Giuseppone N (2023) Daisy chain architectures: From discrete molecular entities to polymer materials. Chem Soc Rev 52:7333\u0026ndash;7358\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSpackman PR, Turner MJ, McKinnon JJ, Wolff SK, Grimwood DJ, Jayatilaka D, Spackman MA (2021) CrystalExplorer: A program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals. J Appl Crystallogr 54:1006\u0026ndash;1011\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTurner MJ, McKinnon JJ, Wolff SK, Grimwood DJ, Spackman PR, Jayatilaka D, Spackman MA (2021) CrystalExplorer 21.5 University of Western Australia\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Scheme 1","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-chemical-crystallography","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jocc","sideBox":"Learn more about [Journal of Chemical Crystallography](http://link.springer.com/journal/10870)","snPcode":"10870","submissionUrl":"https://submission.nature.com/new-submission/10870/3","title":"Journal of Chemical Crystallography","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"di-functionalized pillar[5]arenes, double-threaded dimers, inclusion complexes, supramolecular assembly","lastPublishedDoi":"10.21203/rs.3.rs-8298205/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8298205/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eA1/A2-Asymmetric difunctionalized pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arenes bearing either n-decyloxy and propargyloxy groups or n-octyloxy and propargyloxy groups are synthesized and investigated for their supramolecular assembly behavior under different crystallization conditions. Distinct crystal systems are obtained depending on the co-crystallization medium. Host\u0026ndash;guest inclusion complexes with adiponitrile form when crystallization is carried out from solutions containing adiponitrile, whereas cyclic [\u003cem\u003ec2\u003c/em\u003e] daisy chain (\u0026ldquo;double-threaded dimer\u0026rdquo;) architectures are produced from mixed chloroform/cyclohexane solutions. The resulting supramolecular assemblies are characterized by single crystal X-ray diffraction and Hirshfeld surface analyses. Variation in alkyl chain length (n-decyloxy versus n-octyloxy) on the pillar[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]arene framework exerts a pronounced effect on the non-covalent interactions and the consequent self-assembly modes within the crystal networks.\u003c/p\u003e","manuscriptTitle":"Single-Crystal X-ray Diffraction Study of [c2] Daisy Chains and Inclusion Complexes from A1/A2-Functionalized Pillar[5]arenes with Variable Chain Lengths","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-02 07:17:48","doi":"10.21203/rs.3.rs-8298205/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-02-11T20:49:26+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-11T01:08:14+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-03T18:36:12+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"117490551921537061433769054098882480284","date":"2026-01-31T08:52:19+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"318013308218882062467442427862768577874","date":"2026-01-29T21:07:32+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-01-29T18:59:28+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-12-09T06:36:14+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-12-09T06:33:21+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Chemical Crystallography","date":"2025-12-07T06:51:27+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-chemical-crystallography","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jocc","sideBox":"Learn more about [Journal of Chemical Crystallography](http://link.springer.com/journal/10870)","snPcode":"10870","submissionUrl":"https://submission.nature.com/new-submission/10870/3","title":"Journal of Chemical Crystallography","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"1be37534-c9d3-438a-9c70-71f06d2f429d","owner":[],"postedDate":"February 2nd, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-03-23T16:05:09+00:00","versionOfRecord":{"articleIdentity":"rs-8298205","link":"https://doi.org/10.1007/s10870-026-01090-9","journal":{"identity":"journal-of-chemical-crystallography","isVorOnly":false,"title":"Journal of Chemical Crystallography"},"publishedOn":"2026-03-19 15:58:28","publishedOnDateReadable":"March 19th, 2026"},"versionCreatedAt":"2026-02-02 07:17:48","video":"","vorDoi":"10.1007/s10870-026-01090-9","vorDoiUrl":"https://doi.org/10.1007/s10870-026-01090-9","workflowStages":[]},"version":"v1","identity":"rs-8298205","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8298205","identity":"rs-8298205","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}