N-Bordered Rylene Arches via Programmable Curved π-Extension

N-Bordered Rylene Arches via Programmable Curved π-Extension | 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 Article N-Bordered Rylene Arches via Programmable Curved π-Extension Zhaohui Wang, Kai Chen, Zuoyu Li, Jiangtao Chan, Xuan Jin, Ming-Wei Wang, and 4 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8245215/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Curved molecular carbons have captured significant concerns due to their distinct properties from planar analogues and topologies serving as segments of diverse nonplanar carbon allotropes. Notably, aromatic ribbons featuring continuously and directionally curved π-surface have been theoretically predicted to be critical to circular carbon analogues, but have remained a synthetic challenge in chemistry. Herein, we address the synthesis and properties of arch-shaped N-bordered nanoribbons which feature rylene backbone attached by five-membered rings at the armchair-edges via a programmable curved π-extension strategy. X-ray crystallographic analyses reveal their directionally and continuously curved π-surfaces with arched topologies and high arch-to-arch inversion barrier according to VT 1H NMR and theoretical calculations. Notably, the resultant quaterrylene arch exhibits a boosted Φf in solution compared to planar quaterrylene diimides and can be associated with C60 in solution and solid state. This work opens a pathway for investigating new series of curved graphene nanoribbons and provides an opportunity for the promising synthesis of relevant long-cherished carbon nanobelts. Physical sciences/Chemistry/Organic chemistry/Structure elucidation Physical sciences/Chemistry/Physical chemistry Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction Rylenes, due to their chemical structures resembling ultra-narrow armchair-edged graphene nanoribbons, have recently become a research focus and garnered significant attention in the scientific community. Pioneering work by Scholl, Clar, and Müllen not only established the chemical foundation for rylene derivatives, 1-6 but also paved the way for their extensive applications in organic electronics, photonics, and spintronics. 7-9 The one-dimensional conjugated extension of rylenes holds considerable scientific importance due to their characteristic electronic structures. 10 While synthetically challenging remains, well-developed approaches for achieving this extension have been explored both in solution and on-surface. 11-14 In contrast, the controlled bending of rylenes into armchair-edged carbon nanotubes with near-minimum diameters presents a far greater challenge which approaches the limits of feasibility. 15,16 Especially, Vögtle belts, topologically defined as radially peri-fused tubular rylene arrays, have remained one of the most desired synthetic targets since their conceptualization in 1983. 17 The escalating strain and persistent difficulty in controlling molecular orientation during the construction of curved, conjugated, carbon-rich molecules remain unavoidable challenges in the synthesis of belt-shaped aromatics. 18,19 While single- and double-stranded macrocycles have been reliably synthesized as precursors for such targets, their aromatization has yet to be achieved. 20-22 This limitation stems primarily from thermodynamically unfavorable ring-closure steps and kinetically dominant competing rearrangement pathways. 23,24 Comparingly, the modular (LEGO-inspired) stitching methodology–utilizing pre-aromatic conjugated scaffolds–represents a complementary strategy that circumvents traditional synthetic bottlenecks, in which polycyclic aromatic hydrocarbons incorporated with pentagons are significant for curved π-surfaces formation. 25-27 As a fundamental building block in rylene chemistry, perylene modification have played not only a pivotal role in accessibility of oligomeric fused rylenes and armchair graphene nanoribbons (AGNRs), but also have profound influence on their electronic and photophysical properties as well as topologies. 13,28,29 Recent progress has witnessed the development of curved perylenes by incorporating pentagon rings at both bay-positions, in which perylenes undergo a planar-to-bowl transition with the decrease of carbon- heteroatom covalent radii, stemming from strain-induced curvature. 30-36 Moreover, their longitudinal π-extension resulted in nonplanar ribbons with dynamic wavy conformation, which demonstrates linear growth types and relatively small curvature. 34,36 In 1999, Siegel and coworker theoretically demonstrated that [5]canastane adopt a pronounced directional curved skeleton in which bay-positions are fully annulated by saturated carbons (Figure 2a). A computed high inversion barrier of 44.5 kcal mol -1 implied their conserved curved structure. Anticipatively, Siegel made a prediction that extension of canastanes motif will lead to circular belt and carbon nanocoils without additional strain. 37 However, it is challenging to incorporate multiple pentagons in such confined geometries due to extreme high strain energy. In this work, we report the synthesis and characterization of curved quaterrylene derivative 9 (Figure 2b), achieved through a rational molecular design and synthetic strategy. Owing to the presence of pentagons, both the molecules exhibit arch geometries with directional curved π-surface and they present substantial resistance of planarization. Quaterrylene 9 displays intense fluorescence emission with quantum yield of 79%, and forms host-guest complexation with C 60 both in solution and solid state. This work provides an extremely potential platform to the achievement of long-sought-after Vögtle belts. Results and discussion Design and Synthesis To comprehend the impact of heterocyclization on curvature of the aforementioned curved motif, we optimized the structure of hexapentagons-annulated quarterrylene ( 6X-QR ) by density functional theory (DFT) calculations. The result indicates an overall trend that the shorter the C-X length, the larger the curvature except for sulfur, and therefore the closer to the corresponding belts in the same numbers of naphthalenes (Figs. 1 and 2 a). Accordingly, N- and O-types are the ideal candidates for such curved GNRs. Leveraging the synthetic feasibility and tunable electronic properties of double N-annulated perylenes, 34,35 N-type are expected to be optimal for the motif. From the synthetic aspect, it is challenging to construct multiple pentagons in higher rylenes based on chloro-substituted precursors due to the predictable high ring strain and consequent low yield. In addition, previous work has shown that N-containing intermediates failed to the offer double N-annulated perylenes. 38 Similarly, this phenomenon is observed in tetra-nitrated terylene derivative (Figure S1 ). Therefore, we propose a programmable curved π-extension strategy of structural evolution starting from prebuilt molecular bowl. As illustrated in Fig. 2 b, the crucial procedures include length growth of a molecular bowl (A), post-functionalization of the resultant large bowl (B) and geometrical transformation by additional N-annulations to achieve the N-bordered rylenes (C). Benefiting from the prebuilt bowl core, Cadogan reaction become effective in formation of multiple pentagons. Considering the stability and processibility of relevant compounds, electron-deficient aryl (Ar F ) and imides substituents were introduced. Possibilities for further modification such as Hunsdiecker reaction inspired by classical perylene transformation, 29 which is crucial for further π-extension. As shown in Fig. 2 b, the synthetic routes began with tetrachloroperylene ( 1 ) which has been reported by our group, and in this work double N-annulated perylene ( 2 ) was synthesized up to 10 gram-scale to which electron-withdrawing 3,5-bis(trifluoromethyl)phenyl was introduced. 35 In comparison to reported method 34 , 35 , large-scale preparation of bowl shaped 2 establish it as a promising building block for constructing complex curved architectures. Owing to the resultant electron-deficient perylene core, dibromination of 2 with NBS occurred at 50°C, and subsequent Miyaura reaction offered diboron esters 3 . Notably, intermediate 3 can efficiently react with dibromonaphthalene diesters through Suzuki and C-H transformation tandem reaction to form quaterrylene bowl ( 4 ) in 55% yield (Step A). Due to the protection of ester groups, subsequent nitrification of 4 precisely gave 6 in 99% yield (step B). And aforementioned esters can be readily converted into the imide groups. As delineated above, additional N-annulations were eventually constructed by Cadogan reaction in 60% yield (Step C). Compounds 7 is soluble in various common solvents such as dichloromethane, toluene, THF, ethyl acetate, methanol, DMF, DMSO due to their predictable curved skeletons and polar NH groups. For synthetic convenience, these NH groups were saturated with butyl chains. Further transformations from esters to imides were achieved by successive hydrolysis and imidization to successfully afford 9 in 68% yield over two steps. The molecular structures of compounds 3 – 9 were confirmed by NMR spectroscopy, and mass spectrometry (Supporting Information). X-ray Crystallographic and Conformational Analysis The solid-state structure of 7 and 9 were unambiguously confirmed by crystal X-ray diffraction. As illustrated in Fig. 3 a and 3 c, crystalline 7 and 9 exhibit awaited continuous directional arch-shaped geometry featuring a quaterrylene core and bordered by six pyrrole rings. These curved structures stem from ring strain and the strain energy is calculated to be 176.2 and 193.0 kcal mol − 1 for 7 and 9 , respectively (Figure S12). For the quantitative evaluation and comparison of the curvature of these arches and bowl 2 , 35 the central angles ( θ) and the π-orbital axis vector (POAV) angles of non-planar π-surfaces were investigated according to their definitions in reported literatures. 39 , 40 The θ values of 2 , 7 are measured to be 41°, 149° from crystal data, which are in close proximity to DFT calculated angels, and these results indicate an evolution from minimally bending to highly curved structures by PCE strategy (Fig. 3 a and S7). As further demonstrated by POAV angles, 2 , 7 exhibit largest degrees of 7.1° and 9.2° which reveal local curvature. Intriguingly, the smaller POAV angles (2.6°-4.4° for 2 , 3.0°-7.1° for 7 ) lied at the rim, while the larger values (5.7°-7.1° for 2 , 7.6°-9.2° for 7 ) occurred at the hub of both 2 and 7 (Fig. 2 b and S6). These features identify the positive Gaussian curvature of these π-surfaces. The maximum POAV angle of 7 is larger than corannulene (8.1°) and summanene (8.7°). 41,42 Additionally, the resultant quaterrylene arch is distinct from bowl-shaped aromatics in terms of geometric features and specifically, the arch shows span-to-width ratio up to 1.6. The arch span at the rim, the distances of peri-carbons were measured ranging from 10.6 to 10.8 Å, and the arch width, defined as the distance of the bottom two nitrogen atoms, is 6.44 Å. The arch depth, measured as the distance from the plane formed by peripherial carbon atoms to the centroid of the hub benzene ring, is 4.58 Å. According to DFT results that variations of the substituents at the terminal positions do not significantly affect the curvature (Figure S7), indicating that conformational changes of 9 arise from shape complementarity requirement in host-guest interactions with C 60 . Accordingly, 9 exhibits conformational adaptability that geometric parameters alter upon inclusion with C₆₀, with decrease in the θ and POAV angle to 120° and a maximum of 8.3°, respectively (Fig. 3 d and 3 e). Compound 7 crystallized in the orthorhombic system, adopting the non-centrosymmetric Fdd2 space group, which can be attributed to asymmetric intermolecular hydrogen bonds within orthogonally assembled dimers (Fig. 3 c and S4). Specifically, hydrogen bonds from N-H to carbonyl oxygen with H···O distances ranging from 2.13 Å to 2.40 Å. Additionally, 7 exhibited short contacts with guest molecules including N-H···Cl and C-Cl···π interactions. Beyond the discrete structures dominated by hydrogen bonds, every cage demonstrated π···π interactions between adjacent molecules, the distance of which is 3.35 to 3.47 Å, self-assembling into a three-dimensional structure (Figure S4 ). The inversion process was investigated by variable-temperature (VT) 1 H NMR analysis and DFT calculations, and N-substituents were neglected for computational simplicity. To elucidate the dynamical evolution patterns from molecular bowl to arch, 5 , 7 and 9 were considered at the same level of theory. For quaterrylene bowl ( 5 ), a decrease of the temperature to 258 K resulted in the resolution of the single averaged peak for the 3,5-bis(trifluoromethyl)phenyl aromatic protons into two signals. (a and a*) (Figure S13). This phenomenon indicates a rapid bowl-to-bowl inversion process at room temperature. According to the splitting of the proton signal at 7.45 ppm, the interconversion rate k is estimated to be 314 s − 1 at 268 K, and the inversion barrier was determined to be 12.1 kcal mol − 1 which is slightly lower than the theoretical value of 16.5 kcal mol − 1 (Figure S11). Notably, as the temperature decreased, the 1 H-NMR spectrum of 9 did not show the transition from a singlet through broadening to splitting, which indicates a much larger arch-to-arch inversion barrier (Fig. 4 a). As predicted by theoretical calculations, 9 demonstrates distinct inversion process of two S-shaped transition states with high inversion barrier of 42.2 and 54.4 kcal mol − 1 for TS1 and TS2 (Fig. 4 b). These results show that the PCE strategy for molecular bowls goes beyond structural evolution to profoundly affect molecular dynamics, inducing a transition from a dynamic bowl to relatively static arch architectures. Photophysical and Electrochemical Properties Absorption and fluorescence emission spectroscopy of QDI , 5 and 9 in dilute toluene solution were measured to elucidate the effects of N-annulation on the photophysical properties. As illustrated in Fig. 4 a, a significant blue shift was observed as more pyrrole were introduced. The absorption spectra exhibit distinct maxima at 758nm ( ε = 1.43 × 10 5 M − 1 cm − 1 ), 697 nm ( ε = 1.00 × 10 5 M − 1 cm − 1 ) and 630 nm ( ε = 0.71 × 10 5 M − 1 cm − 1 ) for QDI , 5 and 9 , respectively. And the optical bandgaps ( E g,opt ) were estimated to be 1.55, 1.69 and 1.80 eV for QDI , 5 and 9 according to E g,opt = 1240/ λ onset . Notably, an absorption shoulder appeared at 655 nm for 9 , which is attributed to the excitations to S 1 (with 99% HOMO → LUMO contribution) according to time-dependent DFT (TD-DFT) calculations in Figure S11, as similarly evidenced by the decrease of this peak during the titration with C 60 ( Vide Infra ). The emission maxima for 5 and 9 are centered at 725 and 687 nm, respectively. Moreover, fluorescence spectroscopy demonstrated distinct emission profiles that 5 exhibited two well-resolved vibronic peaks in the near-infrared (NIR) region (660–875 nm), whereas 9 displayed broadened emission bands with dual shoulders spanning 600–875 nm, indicative of altered vibronic coupling due to N-annulations. Notably, the absolute fluorescence quantum yields ( Φ f ) of 5 (26%) and 9 (79%) demonstrated a dramatic enhancement compared to the reported quaterrylene diimides ( Φ f ≈ 1%). 43 The electrochemical properties of compounds 5 and 9 were evaluated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. As shown in Fig. 4 c, one reversible two-electrons reduction wave and two reversible single-electron oxidation waves were observed in both 5 and 9 . Specifically, compound 5 exhibits oxidative half-wave potential of E 1/2 ox1 = 0.38 V, E 1/2 ox2 = 0.74 V and reductive half-wave potentials of E 1/2 re1 = -1.30 V. In comparison to 5, 9 displayed more positive potentials of E 1/2 ox1 = 0.18 V, E 1/2 ox2 = 0.40 V and E 1/2 re1 = -1.63 V, demonstrating that the N-annulation is benefit to electron-rich property. Electrochemical energy levels were estimated to be E LUMO = (-3.50 eV for 5 , -3.17 eV for 9 ) and E HOMO = (-5.18 eV for 5 , -4.98 eV for 9 ), which are elevated compared to QDI 43 (Fig. 4 d). Consequently, the corresponding electrochemical energy gaps of 5 and 9 were calculated to be 1.68 and 1.81 eV which is consistent with their optical bandgaps. Aromaticity The aromaticity variation patterns of QDI , 5 and 9 was investigated by the nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (AICD) calculations (Figure S15a-S15f). The NICS(1) zz scan revealed a pronounced shielding region at the center of the rings A and C with average NICS(1) zz values of -19.03 and − 15.90 ppm for QDI , indicating their strong aromatic characters. While positive NICS(1) zz values of rings B and D implied their anti-aromatic features. The AICD plot demonstrated localized aromaticity of QDI with 10π electrons diamagnetic ring current within each naphthalene subunit. The NICS(1) zz value of ring C in 5 decreases as adjacent pyrrole rings constructed and pyrrole rings exhibit positive values as well, resulting conjugation with 18π (4n + 2) electrons, satisfying Hückel's rule of aromaticity. As directly visualized by the AICD plot of 5 , clockwise ring current featuring 18π electrons occurred in double N-annulated perylene subunit, demonstrating N-annulation-induced expansion of the aromatic domain. Accordingly, NICS(1) zz value of ring A in 9 continually decreases, thus, the aromaticity gains significant strength. Furthermore, AICD plot of 9 illustrated clockwise ring current with 34π (4n + 2) electrons along the periphery of conjugation system containing the lone pair electrons of six nitrogen atoms, indicating a global aromatic character of this highly crved π-skeleton (Figure S15f). While the hub ring D exhibited weak anticlockwise current, meaning its nonaromatic or anti-aromatic characteristic. Supramolecular Interactions with Fullerene C The electron-rich and curved π-surface of quaterrylene arch should facilitate the concave-convex interactions with electron-deficient fullerene, and the supramolecular behaviors between 9 and C 60 were investigated both in solution and solid state. As shown in Figure S7a, the appearance of an isosbestic point in the titration absorption spectrum indicates the formation of a host-guest complex in solution. Further titration experiment of 9 with C 60 in toluene solution was conducted by recording the fluorescence intensity changes at 685 and 745 nm. Fluorescence quenching occurred when adding C 60 into solution of 9 , indicating efficient energy transfer from 9 to C 60 . The titration data analysis supported a 1:1 binding model, and the association constant ( K a ) was estimated to be 6.97 × 10 5 M − 1 (Figure S7c), which is larger than perylene bowls and giant molecular bowls. 34 , 35 , 44 – 47 The crystal structure of 9@C 60 was unambiguously verified by X-ray diffraction, and it revealed 1:1 stoichiometry in line with the observation in solution (Figure S5). In solid state, C 60 and 9 reciprocally interact in a complementary concave-convex geometry. Intriguingly, the quaterrylene arch adapts its central angle ( θ ) to 120° for optimal contact with C 60 (Fig. 3 d and 3 f), which indicates a peripheral vibration. The closest distance between C 60 and 9 is 3.19 Å, demonstrating the presence of strong π-π interactions (Figure S3 f). Additionally, there exists convex-convex contacts at distances of 3.30 Å to form C 60 and arch arrays along the a axis (Figure S5). Along the c axis, 9 orientated reversely to form wavy arrays with convex-convex π-π interactions at distances ranging from 3.17 to 3.35 Å. Accordingly, this close-packed long-range ordered stacking might provide multiple channels for effective charge transportation which play an important role in organic electronics devices. Conclusion In summary, we present a programmable curved π-extension strategy of structural evolution from a bowl to arches with continuous directional curved topologies, highlighting N-bordered quaterrylene motifs achieved by effective Cadogan reaction as a crucial step. X-ray crystallographic analysis undoubtedly confirms the highly curved arch geometry with positive Gaussian curvature. Moreover, quaterrylene arch demonstrates high arch-to-arch inversion barrier which has been evident from VT 1 H NMR and DFT calculations. Notably, the resultant arch exhibits excellent Φ f up to 79% representing the highest among quaterrylene derivatives. Furthermore, the arch can engage in host-guest complexation with C 60 and co-assembled into tightly associated assemblies. These unique topological rylene-based molecular carbons might provide a potential platform to achieve long-sought-after Vögtle belts. Future work in our laboratory will focus on the functionalization and subsequent “stitching” of these arch units. Methods Synthesis of compound 4 A 350 mL Schlenk flask was charged with 3 (954 mg, 1 mmol), 1,8-dibromo-4,5-di-n-butyl-naphthalenedicarboxylate (1.12 g, 2.3 mmol), Pd 2 (dba) 3 (183 mg, 0.2 mmol), PCy 3 (224 mg, 0.8 mmol), K 2 CO 3 (1.66 g, 12 mmol) and super dry o -xylene (100 mL) under argon. The mixture was heated to 145 º C with vigorous stirring for 36 h. The cooled mixture was purified by column chromatography on silica gel, eluted with CH 2 Cl 2 /EA = 500:1 then recrystallized through methanol to afford 4 as a slate blue solid (740 mg, 55% yield). Synthesis of compound 4 A 350 mL Schlenk flask was charged with 3 (954 mg, 1 mmol), 1,8-dibromo-4,5-di-n-butyl-naphthalenedicarboxylate (1.12 g, 2.3 mmol), Pd 2 (dba) 3 (183 mg, 0.2 mmol), PCy 3 (224 mg, 0.8 mmol), K 2 CO 3 (1.66 g, 12 mmol) and super dry o -xylene (100 mL) under argon. The mixture was heated to 145 º C with vigorous stirring for 36 h. The cooled mixture was purified by column chromatography on silica gel, eluted with CH 2 Cl 2 /EA = 500:1 then recrystallized through methanol to afford 4 as a slate blue solid (740 mg, 55% yield). Synthesis of compound 6 A 500 mL flask was charged with 4 (820 mg, 0.54 mmol) and dissolved in CH 2 Cl 2 (170 mL), then tert-Butyl nitrite (1.8 mL, 13 mmol) was added. The mixture was stirred at room temperature for 4.5 h. The mixture was purified by flash chromatography on silica gel with CH 2 Cl 2 then recrystallized through methanol to afford 6 as a violet solid (920 mg, 99% yield). Synthesis of compound 7 A 350 mL Schlenk flask was charged with 6 (923 mg, 0.6 mmol), PPh 3 (4.43 g, 16.8 mmol) and super dry 1,2-dichlorobenzene (92 mL) under argon. The mixture was stirred at 160 ºC for 12 h. The cooled mixture was purified by column chromatography on silica gel, eluted with CH 2 Cl 2 /EA = 200:1 then CH 2 Cl 2 /EA = 50:1, then recrystallized through petroleum ether to afford 7 as a brick red solid (440 mg, 60% yield). Synthesis of compound 5 A 100 mL Schlenk flask was charged with 4 (326 mg, 0.24 mmol), KOH (337 mg, 6 mmol), and tert-butanol (39 mL) under argon. The mixture was stirred at 85 º C for 12 h. After cooling to room temperature, 75mL 1M hydrochloric acid was added at 0 º C and stirred for 10 min, then the precipitate was collected by vacuum filtration. 23mL acetic acid was added to the filtrated solid stirring for 3h before 30ml water was added to the mixture, then the precipitate was collected by vacuum filtration to get a purplish gray solid as an intermediate for directly use. A 100 mL Schlenk flask was charged with the intermediate (109 mg, 0.1 mmol), 1-phenylethylamine (103 µL, 0.8 mmol), imidazole (1.8g), and catalytic amount of zinc acetate under argon. The mixture was stirred at 140 º C for 12 h. After cooling to room temperature, 5mL 1M hydrochloric acid was added and stirred, then the precipitate was collected by vacuum filtration. The mixture was purified by column chromatography on silica gel, eluted with CH 2 Cl 2 , then recrystallized through methanol to afford 5 as a blue-violet solid (90 mg, 70% yield). Synthesis of compound 9 A 100 mL Schlenk flask was charged with 8 (244 mg, 0.15 mmol), KOH (427 mg, 7.6 mmol), and tert-butanol (24 mL) under argon. The mixture was stirred at 85 º C for 12 h. After cooling to room temperature, 50mL 1M hydrochloric acid was added at 0 º C and stirred for 10 min, then the precipitate was collected by vacuum filtration. 15 mL acetic acid was added to the filtrated solid stirring for 3 h before 30 mL water was added to the mixture, and the precipitate was collected by vacuum filtration to get a purplish gray solid as an intermediate for directly use. A 100 mL Schlenk flask was charged with the intermediate (198 mg, 0.145 mmol), 1-phenylethylamine (113 µL, 0.87 mmol), imidazole (3.2 g), and catalytic amount of zinc acetate under argon. The mixture was stirred at 140 º C for 12 h. After cooling to room temperature, 10 mL 1M hydrochloric acid was added and stirred, then the precipitate was collected by vacuum filtration. The mixture was purified by column chromatography on silica gel, eluted with petroleum ether/CH 2 Cl 2 = 1:3, then recrystallized through methanol to afford 9 as a purple-gray solid (155 mg, 68% yield). Declarations Data availability Crystallographic data for the structure reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2504268 for 7 and CCDC 2504270 for 9@C60 . Copies of the data can be obtained free of charge via https://www.ccdc. cam.ac.uk/structures/. The authors declare that the data supporting the findings of this study are available within the paper, the source data and Supplementary Information files. Source data are provided with this paper. Acknowledgements This work was financially supported by the National Natural Science Foundation of China (No. 22350005 and 22235005). The authors thank Tsinghua Xuetang Talents Program for providing the theoretical calculation resources. Author information These authors contributed equally: Kai Chen, Zuoyu Li. Authors and Affiliations Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China Kai Chen, Zuoyu Li, Jiangtao Chan, Ming-Wei Wang, Xu Wen, Zixin Liu & Zhaohui Wang School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China Kai Chen, Wei Jiang Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East ChinaUniversity of Science and Technology, Shanghai 200237, China Xuan Jin, Guogang Liu Author contributions Z. W. conceived and supervised the study, and finalized the manuscript. Z. W., W. J., and G. L. participated in scientific discussions and data interpretation. K. C. and Zuoyu Li performed synthetic works. J. C. performed single-crystal X-ray diffraction study. K. C. and X. W. performed physical characterizations. K. C., Zuoyu Li, M. -W. W. and Zixin Liu performed computational studies. X. J. assisted with the scale-up synthesis of compound 1 . Corresponding authors Correspondence to Zhaohui Wang, [email protected] Competing interests The authors declare no competing interests. Additional information Supporting information Source Data Fig. 4 References Scholl R, Seer C, Weitzenböck R (1910) Perylen, ein hoch kondensierter aromatischer Kohlenwasserstoff C 20 H 12 . Ber Dtsch Chem Ges 43:2202–2209 Clar E (1948) Oligomers of peri-condensed naphthylens have been termed rylenes. Chem. Ber. 81, 52 – 63 Bohnen A, Koch KH, Lüttke W, Müllen K (1990) Oligorylene als Modelle für „Poly (peri-naphthalin). 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Supplementary Files checkcif.pdf Checkcif SourceDataFig.4.xlsx Source Data Fig. 4 2504268.cif Crystallographic data for compoud 7 2504270.cif Crystallographic data for 9@C60 SupportingInformation.docx Supporting Information Cite Share Download PDF Status: Under Review Version 1 posted 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. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-8245215","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":570997811,"identity":"4ea2923c-e5ca-4595-aa76-7be5d2e6ef6f","order_by":0,"name":"Zhaohui 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blue).\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/4a25a5d4a81844ae8ffdb9ee.png"},{"id":99858221,"identity":"180fac3c-5e7b-4b8f-9e57-e80d140d8f45","added_by":"auto","created_at":"2026-01-09 06:24:57","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1155440,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Siegle’s molecular model \u003cstrong\u003e[5]canastane\u003c/strong\u003e and \u003cstrong\u003e6X-QR\u003c/strong\u003e proposed in this work presented by optimized structures of \u003cstrong\u003e6X-QR\u003c/strong\u003e with different curvature evaluated by central angles (\u003cem\u003eθ\u003c/em\u003e)\u003csup\u003e39\u003c/sup\u003e (all substituents are omitted for clarity). (b) Synthetic routes to curved quaterrylene dimides \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e.\u003cstrong\u003e \u003c/strong\u003eReaction conditions: (ⅰ) Ar\u003csub\u003eF\u003c/sub\u003eNH\u003csub\u003e2\u003c/sub\u003e, Pd(P\u003csup\u003et\u003c/sup\u003eBu\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e, \u003csup\u003et\u003c/sup\u003eBuONa, \u003cem\u003eo\u003c/em\u003e-xylene, 120°C, 12h, 30%. (ⅱ) 1) NBS, DCE, 50 °C, 12h; 2) (Bpin)\u003csub\u003e2\u003c/sub\u003e, Pd(dppf)Cl\u003csub\u003e2\u003c/sub\u003e, KOAc, dioxane, 100 °C, 36h, 51% over two steps. (ⅲ) Pd\u003csub\u003e2\u003c/sub\u003e(dba)\u003csub\u003e3\u003c/sub\u003e, PCy\u003csub\u003e3\u003c/sub\u003e, K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e, \u003cem\u003eo\u003c/em\u003e-xylene, 145 °C, 36 h, 55%; (iv) KOH, \u003csup\u003et\u003c/sup\u003eBuOH, reflux, 24h, then AcOH , 3h at r.t.; 2) \u003cem\u003eα\u003c/em\u003e-methylbenzylamine, Zn(OAc)\u003csub\u003e2\u003c/sub\u003e, imidazole, 140 °C, 24h, 50% over two steps. (ⅴ) \u003csup\u003et\u003c/sup\u003eBuONO, CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, rt, 12h, 99%; (ⅵ) PPh\u003csub\u003e3\u003c/sub\u003e, \u003cem\u003eo\u003c/em\u003e-DCB, 160 °C, 12h, 60%. (ⅶ) \u003csup\u003en\u003c/sup\u003eBuBr, K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e, DMF, 120 °C, 12h, 60%; (ⅷ) 1) KOH, \u003csup\u003et\u003c/sup\u003eBuOH, reflux, 24h, then AcOH , 3h at r.t.; 2) \u003cem\u003eα\u003c/em\u003e-methylbenzylamine, Zn(OAc)\u003csub\u003e2\u003c/sub\u003e, imidazole, 140 °C, 24h, 68% over two steps. Programmable Curved π-Extension (PCE): steps \u003cstrong\u003eA\u003c/strong\u003e, \u003cstrong\u003eB\u003c/strong\u003e and \u003cstrong\u003eC\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/4060b9147d6dc810a7ce1621.png"},{"id":100357603,"identity":"93ebef66-6ec6-4279-9941-0d1d641bc4f2","added_by":"auto","created_at":"2026-01-16 07:20:06","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1105103,"visible":true,"origin":"","legend":"\u003cp\u003eX-ray crystal structure of \u003cstrong\u003e7 \u003c/strong\u003e(a-c)\u003cstrong\u003e \u003c/strong\u003eand\u003cstrong\u003e 9 \u003c/strong\u003e(d-f): (a, d) side view (b, e) top view and POAV angles, (c) (f) \u003cstrong\u003e9@C\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e60\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e.\u003c/strong\u003e Ellipsoids are set at 50 % probability. All hydrogen atoms and substituents are omitted for clarity and geometric parameters are shown. The structure of compound \u003cstrong\u003e9\u003c/strong\u003e was determined from its co-crystal with C\u003csub\u003e60\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/5fc620225897a075b408d5e4.png"},{"id":99858224,"identity":"c8766e00-a8f7-44a9-a862-f854fa93205a","added_by":"auto","created_at":"2026-01-09 06:24:57","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":806264,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Absorption spectra of \u003cstrong\u003eQDI\u003c/strong\u003e, \u003cstrong\u003e5\u003c/strong\u003eand \u003cstrong\u003e9\u003c/strong\u003e. (b) Fluorescence spectra and of \u003cstrong\u003e5\u003c/strong\u003e and \u003cstrong\u003e9\u003c/strong\u003e. (c) Cyclic voltammetry and differential pulse voltammetry curves of \u003cstrong\u003e5\u003c/strong\u003e and \u003cstrong\u003e9\u003c/strong\u003e. (d) Electrochemical energy level diagram of \u003cstrong\u003eQDI\u003c/strong\u003e, \u003cstrong\u003e5\u003c/strong\u003e and\u003cstrong\u003e 9\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/75a5877957f1493a8e64a1a9.png"},{"id":100379944,"identity":"ed1cd37e-4000-40b8-b513-78de8bc0faa5","added_by":"auto","created_at":"2026-01-16 09:56:38","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5649601,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/d4e787b2-6f35-4f5d-9a9f-7afa9052318e.pdf"},{"id":99858219,"identity":"17981eca-ce62-44aa-acb1-a0f7646faff3","added_by":"auto","created_at":"2026-01-09 06:24:57","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":238111,"visible":true,"origin":"","legend":"Checkcif","description":"","filename":"checkcif.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/1e8d4ac2b4771ffe268e01a6.pdf"},{"id":100357978,"identity":"1c5caaaa-c40f-4052-bf29-24bc5bb8975c","added_by":"auto","created_at":"2026-01-16 07:20:32","extension":"xlsx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":328720,"visible":true,"origin":"","legend":"Source Data Fig. 4","description":"","filename":"SourceDataFig.4.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/bcd85d74a0f621a52202e87e.xlsx"},{"id":99858226,"identity":"fe7dc709-a926-4d2e-ae3a-498781326ccb","added_by":"auto","created_at":"2026-01-09 06:24:57","extension":"cif","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":1113161,"visible":true,"origin":"","legend":"Crystallographic data for compoud 7","description":"","filename":"2504268.cif","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/e1d49816f58b991929eea04b.cif"},{"id":100357631,"identity":"01c59afb-e583-45b9-91fa-b57f6b36f0e6","added_by":"auto","created_at":"2026-01-16 07:20:07","extension":"cif","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":5455097,"visible":true,"origin":"","legend":"Crystallographic data for 9@C60","description":"","filename":"2504270.cif","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/229e97a4dec93a9b9f3be876.cif"},{"id":99858233,"identity":"1fc4873d-4057-4ef9-a5ca-aa721080bc4c","added_by":"auto","created_at":"2026-01-09 06:24:57","extension":"docx","order_by":5,"title":"","display":"","copyAsset":false,"role":"supplement","size":7089950,"visible":true,"origin":"","legend":"Supporting Information","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-8245215/v1/f146e375af98af69084da851.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"N-Bordered Rylene Arches via Programmable Curved π-Extension","fulltext":[{"header":"Introduction","content":"\u003cp\u003eRylenes, due to their chemical structures resembling ultra-narrow armchair-edged graphene nanoribbons, have recently become a research focus and garnered significant attention in the scientific community. Pioneering work by Scholl, Clar, and M\u0026uuml;llen not only established the chemical foundation for rylene derivatives,\u003csup\u003e1-6\u003c/sup\u003e but also paved the way for their extensive applications in organic electronics, photonics, and spintronics.\u003csup\u003e7-9\u003c/sup\u003e The one-dimensional conjugated extension of rylenes holds considerable scientific importance due to their characteristic electronic structures.\u003csup\u003e10\u003c/sup\u003e While synthetically challenging remains, well-developed approaches for achieving this extension have been explored both in solution and on-surface.\u003csup\u003e11-14\u003c/sup\u003e In contrast, the controlled bending of rylenes into armchair-edged carbon nanotubes with near-minimum diameters presents a far greater challenge which approaches the limits of feasibility.\u003csup\u003e15,16\u003c/sup\u003e Especially, V\u0026ouml;gtle belts, topologically defined as radially peri-fused tubular rylene arrays, have remained one of the most desired synthetic targets since their conceptualization in 1983.\u003csup\u003e17\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eThe escalating strain and persistent difficulty in controlling molecular orientation during the construction of curved, conjugated, carbon-rich molecules remain unavoidable challenges in the synthesis of belt-shaped aromatics.\u003csup\u003e18,19\u003c/sup\u003e While single- and double-stranded macrocycles have been reliably synthesized as precursors for such targets, their aromatization has yet to be achieved.\u003csup\u003e20-22\u003c/sup\u003e This limitation stems primarily from thermodynamically unfavorable ring-closure steps and kinetically dominant competing rearrangement pathways.\u003csup\u003e23,24\u003c/sup\u003e Comparingly, the modular (LEGO-inspired) stitching methodology\u0026ndash;utilizing pre-aromatic conjugated scaffolds\u0026ndash;represents a complementary strategy that circumvents traditional synthetic bottlenecks, in which polycyclic aromatic hydrocarbons incorporated with pentagons are significant for curved \u0026pi;-surfaces formation.\u003csup\u003e\u0026nbsp;25-27\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eAs a fundamental building block in rylene chemistry, perylene modification have played not only a pivotal role in accessibility of oligomeric fused rylenes and armchair graphene nanoribbons (AGNRs), but also have profound influence on their electronic and photophysical properties as well as topologies.\u003csup\u003e13,28,29\u003c/sup\u003e Recent progress has witnessed the development of curved perylenes by incorporating pentagon rings at both bay-positions, in which perylenes undergo a planar-to-bowl transition with the decrease of carbon- heteroatom covalent radii, stemming from strain-induced curvature.\u003csup\u003e30-36\u003c/sup\u003e Moreover, their longitudinal \u0026pi;-extension resulted in nonplanar ribbons with dynamic wavy conformation, which demonstrates linear growth types and relatively small curvature.\u003csup\u003e34,36\u003c/sup\u003e In\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e1999, Siegel and coworker theoretically demonstrated that [5]canastane adopt a pronounced directional curved skeleton in which bay-positions are fully annulated by saturated carbons (Figure 2a). A computed high inversion barrier of 44.5 kcal mol\u003csup\u003e-1\u003c/sup\u003e implied their conserved curved structure. Anticipatively, Siegel made a prediction that extension of canastanes motif will lead to circular belt and carbon nanocoils without additional strain.\u003csup\u003e37\u003c/sup\u003e However, it is challenging to incorporate multiple pentagons in such confined geometries due to extreme high strain energy. In this work, we report the synthesis and characterization of curved quaterrylene derivative \u003cstrong\u003e9\u0026nbsp;\u003c/strong\u003e(Figure 2b), achieved through a rational molecular design and synthetic strategy. Owing to the presence of pentagons, both the molecules exhibit arch geometries with directional curved \u0026pi;-surface and they present substantial resistance of planarization. Quaterrylene \u003cstrong\u003e9\u003c/strong\u003e displays intense fluorescence emission with quantum yield of 79%, and forms host-guest complexation with C\u003csub\u003e60\u003c/sub\u003e both in solution and solid state. This work provides an extremely potential platform to the achievement of long-sought-after V\u0026ouml;gtle belts.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec2\" class=\"Section2\"\u003e \u003ch2\u003eDesign and Synthesis\u003c/h2\u003e \u003cp\u003eTo comprehend the impact of heterocyclization on curvature of the aforementioned curved motif, we optimized the structure of hexapentagons-annulated quarterrylene (\u003cb\u003e6X-QR\u003c/b\u003e) by density functional theory (DFT) calculations. The result indicates an overall trend that the shorter the C-X length, the larger the curvature except for sulfur, and therefore the closer to the corresponding belts in the same numbers of naphthalenes (Figs.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea). Accordingly, N- and O-types are the ideal candidates for such curved GNRs. Leveraging the synthetic feasibility and tunable electronic properties of double N-annulated perylenes,\u003csup\u003e34,35\u003c/sup\u003e N-type are expected to be optimal for the motif. From the synthetic aspect, it is challenging to construct multiple pentagons in higher rylenes based on chloro-substituted precursors due to the predictable high ring strain and consequent low yield. In addition, previous work has shown that N-containing intermediates failed to the offer double N-annulated perylenes.\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e Similarly, this phenomenon is observed in tetra-nitrated terylene derivative (Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTherefore, we propose a programmable curved π-extension strategy of structural evolution starting from prebuilt molecular bowl. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb, the crucial procedures include length growth of a molecular bowl (A), post-functionalization of the resultant large bowl (B) and geometrical transformation by additional N-annulations to achieve the N-bordered rylenes (C). Benefiting from the prebuilt bowl core, Cadogan reaction become effective in formation of multiple pentagons. Considering the stability and processibility of relevant compounds, electron-deficient aryl (Ar\u003csub\u003eF\u003c/sub\u003e) and imides substituents were introduced. Possibilities for further modification such as Hunsdiecker reaction inspired by classical perylene transformation,\u003csup\u003e29\u003c/sup\u003e which is crucial for further π-extension.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb, the synthetic routes began with tetrachloroperylene (\u003cb\u003e1\u003c/b\u003e) which has been reported by our group, and in this work double N-annulated perylene (\u003cb\u003e2\u003c/b\u003e) was synthesized up to 10 gram-scale to which electron-withdrawing 3,5-bis(trifluoromethyl)phenyl was introduced.\u003csup\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e In comparison to reported method\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e, large-scale preparation of bowl shaped \u003cb\u003e2\u003c/b\u003e establish it as a promising building block for constructing complex curved architectures. Owing to the resultant electron-deficient perylene core, dibromination of \u003cb\u003e2\u003c/b\u003e with NBS occurred at 50\u0026deg;C, and subsequent Miyaura reaction offered diboron esters \u003cb\u003e3\u003c/b\u003e. Notably, intermediate \u003cb\u003e3\u003c/b\u003e can efficiently react with dibromonaphthalene diesters through Suzuki and C-H transformation tandem reaction to form quaterrylene bowl (\u003cb\u003e4\u003c/b\u003e) in 55% yield (Step A). Due to the protection of ester groups, subsequent nitrification of \u003cb\u003e4\u003c/b\u003e precisely gave \u003cb\u003e6\u003c/b\u003e in 99% yield (step B). And aforementioned esters can be readily converted into the imide groups. As delineated above, additional N-annulations were eventually constructed by Cadogan reaction in 60% yield (Step C). Compounds \u003cb\u003e7\u003c/b\u003e is soluble in various common solvents such as dichloromethane, toluene, THF, ethyl acetate, methanol, DMF, DMSO due to their predictable curved skeletons and polar NH groups. For synthetic convenience, these NH groups were saturated with butyl chains. Further transformations from esters to imides were achieved by successive hydrolysis and imidization to successfully afford \u003cb\u003e9\u003c/b\u003e in 68% yield over two steps. The molecular structures of compounds \u003cb\u003e3\u003c/b\u003e\u0026ndash;\u003cb\u003e9\u003c/b\u003e were confirmed by NMR spectroscopy, and mass spectrometry (Supporting Information).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eX-ray Crystallographic and Conformational Analysis\u003c/h2\u003e \u003cp\u003eThe solid-state structure of \u003cb\u003e7\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e were unambiguously confirmed by crystal X-ray diffraction. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec, crystalline \u003cb\u003e7\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e exhibit awaited continuous directional arch-shaped geometry featuring a quaterrylene core and bordered by six pyrrole rings. These curved structures stem from ring strain and the strain energy is calculated to be 176.2 and 193.0 kcal mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for \u003cb\u003e7\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e, respectively (Figure S12). For the quantitative evaluation and comparison of the curvature of these arches and bowl \u003cb\u003e2\u003c/b\u003e,\u003csup\u003e35\u003c/sup\u003e the central angles (\u003cem\u003eθ)\u003c/em\u003e and the π-orbital axis vector (POAV) angles of non-planar π-surfaces were investigated according to their definitions in reported literatures.\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e,\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e The \u003cem\u003eθ\u003c/em\u003e values of \u003cb\u003e2\u003c/b\u003e, \u003cb\u003e7\u003c/b\u003e are measured to be 41\u0026deg;, 149\u0026deg; from crystal data, which are in close proximity to DFT calculated angels, and these results indicate an evolution from minimally bending to highly curved structures by PCE strategy (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea and S7). As further demonstrated by POAV angles, \u003cb\u003e2\u003c/b\u003e, \u003cb\u003e7\u003c/b\u003e exhibit largest degrees of 7.1\u0026deg; and 9.2\u0026deg; which reveal local curvature. Intriguingly, the smaller POAV angles (2.6\u0026deg;-4.4\u0026deg; for \u003cb\u003e2\u003c/b\u003e, 3.0\u0026deg;-7.1\u0026deg; for \u003cb\u003e7\u003c/b\u003e) lied at the rim, while the larger values (5.7\u0026deg;-7.1\u0026deg; for \u003cb\u003e2\u003c/b\u003e, 7.6\u0026deg;-9.2\u0026deg; for \u003cb\u003e7\u003c/b\u003e) occurred at the hub of both \u003cb\u003e2\u003c/b\u003e and \u003cb\u003e7\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb and S6). These features identify the positive Gaussian curvature of these π-surfaces. The maximum POAV angle of \u003cb\u003e7\u003c/b\u003e is larger than corannulene (8.1\u0026deg;) and summanene (8.7\u0026deg;).\u003csup\u003e41,42\u003c/sup\u003e Additionally, the resultant quaterrylene arch is distinct from bowl-shaped aromatics in terms of geometric features and specifically, the arch shows span-to-width ratio up to 1.6. The arch span at the rim, the distances of peri-carbons were measured ranging from 10.6 to 10.8 \u0026Aring;, and the arch width, defined as the distance of the bottom two nitrogen atoms, is 6.44 \u0026Aring;. The arch depth, measured as the distance from the plane formed by peripherial carbon atoms to the centroid of the hub benzene ring, is 4.58 \u0026Aring;. According to DFT results that variations of the substituents at the terminal positions do not significantly affect the curvature (Figure S7), indicating that conformational changes of \u003cb\u003e9\u003c/b\u003e arise from shape complementarity requirement in host-guest interactions with C\u003csub\u003e60\u003c/sub\u003e. Accordingly, \u003cb\u003e9\u003c/b\u003e exhibits conformational adaptability that geometric parameters alter upon inclusion with C₆₀, with decrease in the \u003cem\u003eθ\u003c/em\u003e and POAV angle to 120\u0026deg; and a maximum of 8.3\u0026deg;, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee).\u003c/p\u003e \u003cp\u003eCompound \u003cb\u003e7\u003c/b\u003e crystallized in the orthorhombic system, adopting the non-centrosymmetric \u003cem\u003eFdd2\u003c/em\u003e space group, which can be attributed to asymmetric intermolecular hydrogen bonds within orthogonally assembled dimers (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec and S4). Specifically, hydrogen bonds from N-H to carbonyl oxygen with H\u0026middot;\u0026middot;\u0026middot;O distances ranging from 2.13 \u0026Aring; to 2.40 \u0026Aring;. Additionally, \u003cb\u003e7\u003c/b\u003e exhibited short contacts with guest molecules including N-H\u0026middot;\u0026middot;\u0026middot;Cl and C-Cl\u0026middot;\u0026middot;\u0026middot;π interactions. Beyond the discrete structures dominated by hydrogen bonds, every cage demonstrated π\u0026middot;\u0026middot;\u0026middot;π interactions between adjacent molecules, the distance of which is 3.35 to 3.47 \u0026Aring;, self-assembling into a three-dimensional structure (Figure \u003cspan refid=\"MOESM4\" class=\"InternalRef\"\u003eS4\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe inversion process was investigated by variable-temperature (VT) \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR analysis and DFT calculations, and N-substituents were neglected for computational simplicity. To elucidate the dynamical evolution patterns from molecular bowl to arch, \u003cb\u003e5\u003c/b\u003e, \u003cb\u003e7\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e were considered at the same level of theory. For quaterrylene bowl (\u003cb\u003e5\u003c/b\u003e), a decrease of the temperature to 258 K resulted in the resolution of the single averaged peak for the 3,5-bis(trifluoromethyl)phenyl aromatic protons into two signals. (a and a*) (Figure\u003c/p\u003e \u003cp\u003eS13). This phenomenon indicates a rapid bowl-to-bowl inversion process at room temperature. According to the splitting of the proton signal at 7.45 ppm, the interconversion rate \u003cem\u003ek\u003c/em\u003e is estimated to be 314 s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 268 K, and the inversion barrier was determined to be 12.1 kcal mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e which is slightly lower than the theoretical value of 16.5 kcal mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Figure S11). Notably, as the temperature decreased, the \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH-NMR spectrum of \u003cb\u003e9\u003c/b\u003e did not show the transition from a singlet through broadening to splitting, which indicates a much larger arch-to-arch inversion barrier (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). As predicted by theoretical calculations, \u003cb\u003e9\u003c/b\u003e demonstrates distinct inversion process of two S-shaped transition states with high inversion barrier of 42.2 and 54.4 kcal mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for TS1 and TS2 (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb). These results show that the PCE strategy for molecular bowls goes beyond structural evolution to profoundly affect molecular dynamics, inducing a transition from a dynamic bowl to relatively static arch architectures.\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003ePhotophysical and Electrochemical Properties\u003c/h3\u003e\n\u003cp\u003eAbsorption and fluorescence emission spectroscopy of \u003cb\u003eQDI\u003c/b\u003e, \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e in dilute toluene solution were measured to elucidate the effects of N-annulation on the photophysical properties. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, a significant blue shift was observed as more pyrrole were introduced. The absorption spectra exhibit distinct maxima at 758nm (\u003cem\u003eε\u003c/em\u003e\u0026thinsp;=\u0026thinsp;1.43 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), 697 nm (\u003cem\u003eε\u003c/em\u003e\u0026thinsp;=\u0026thinsp;1.00 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and 630 nm (\u003cem\u003eε\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.71 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for \u003cb\u003eQDI\u003c/b\u003e, \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e, respectively. And the optical bandgaps (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eg,opt\u003c/sub\u003e) were estimated to be 1.55, 1.69 and 1.80 eV for \u003cb\u003eQDI\u003c/b\u003e, \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e according to \u003cem\u003eE\u003c/em\u003e\u003csub\u003eg,opt\u003c/sub\u003e = 1240/\u003cem\u003eλ\u003c/em\u003e\u003csub\u003eonset\u003c/sub\u003e. Notably, an absorption shoulder appeared at 655 nm for \u003cb\u003e9\u003c/b\u003e, which is attributed to the excitations to S\u003csub\u003e1\u003c/sub\u003e (with 99% HOMO \u0026rarr; LUMO contribution) according to time-dependent DFT (TD-DFT) calculations in Figure S11, as similarly evidenced by the decrease of this peak during the titration with C\u003csub\u003e60\u003c/sub\u003e (\u003cem\u003eVide Infra\u003c/em\u003e). The emission maxima for \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e are centered at 725 and 687 nm, respectively. Moreover, fluorescence spectroscopy demonstrated distinct emission profiles that \u003cb\u003e5\u003c/b\u003e exhibited two well-resolved vibronic peaks in the near-infrared (NIR) region (660\u0026ndash;875 nm), whereas \u003cb\u003e9\u003c/b\u003e displayed broadened emission bands with dual shoulders spanning 600\u0026ndash;875 nm, indicative of altered vibronic coupling due to N-annulations. Notably, the absolute fluorescence quantum yields (\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003ef\u003c/sub\u003e) of \u003cb\u003e5\u003c/b\u003e (26%) and \u003cb\u003e9\u003c/b\u003e (79%) demonstrated a dramatic enhancement compared to the reported quaterrylene diimides (\u003cem\u003eΦ\u003c/em\u003e\u003csub\u003ef\u003c/sub\u003e\u0026thinsp;\u0026asymp;\u0026thinsp;1%).\u003csup\u003e43\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe electrochemical properties of compounds \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e were evaluated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec, one reversible two-electrons reduction wave and two reversible single-electron\u003c/p\u003e \u003cp\u003eoxidation waves were observed in both \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e. Specifically, compound \u003cb\u003e5\u003c/b\u003e exhibits oxidative half-wave potential of \u003cem\u003eE\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e\u003csup\u003eox1\u003c/sup\u003e = 0.38 V, \u003cem\u003eE\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e\u003csup\u003eox2\u003c/sup\u003e = 0.74 V and reductive half-wave potentials of \u003cem\u003eE\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e\u003csup\u003ere1\u003c/sup\u003e = -1.30 V. In comparison to 5, 9 displayed more positive potentials of \u003cem\u003eE\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e\u003csup\u003eox1\u003c/sup\u003e = 0.18 V, \u003cem\u003eE\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e\u003csup\u003eox2\u003c/sup\u003e = 0.40 V and \u003cem\u003eE\u003c/em\u003e\u003csub\u003e1/2\u003c/sub\u003e\u003csup\u003ere1\u003c/sup\u003e = -1.63 V, demonstrating that the N-annulation is benefit to electron-rich property. Electrochemical energy levels were estimated to be \u003cem\u003eE\u003c/em\u003e\u003csub\u003eLUMO\u003c/sub\u003e = (-3.50 eV for \u003cb\u003e5\u003c/b\u003e, -3.17 eV for \u003cb\u003e9\u003c/b\u003e) and \u003cem\u003eE\u003c/em\u003e\u003csub\u003eHOMO\u003c/sub\u003e = (-5.18 eV for \u003cb\u003e5\u003c/b\u003e, -4.98 eV for \u003cb\u003e9\u003c/b\u003e), which are elevated compared to QDI\u003csup\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). Consequently, the corresponding electrochemical energy gaps of \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e were calculated to be 1.68 and 1.81 eV which is consistent with their optical bandgaps.\u003c/p\u003e\n\u003ch3\u003eAromaticity\u003c/h3\u003e\n\u003cp\u003eThe aromaticity variation patterns of \u003cb\u003eQDI\u003c/b\u003e, \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e9\u003c/b\u003e was investigated by the nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (AICD) calculations (Figure S15a-S15f). The NICS(1)\u003csub\u003ezz\u003c/sub\u003e scan revealed a pronounced shielding region at the center of the rings A and C with average NICS(1)\u003csub\u003ezz\u003c/sub\u003e values of -19.03 and \u0026minus;\u0026thinsp;15.90 ppm for \u003cb\u003eQDI\u003c/b\u003e, indicating their strong aromatic characters. While positive NICS(1)\u003csub\u003ezz\u003c/sub\u003e values of rings B and D implied their anti-aromatic features. The AICD plot demonstrated localized aromaticity of \u003cb\u003eQDI\u003c/b\u003e with 10π electrons diamagnetic ring current within each naphthalene subunit. The NICS(1)\u003csub\u003ezz\u003c/sub\u003e value of ring C in \u003cb\u003e5\u003c/b\u003e decreases as adjacent pyrrole rings constructed and pyrrole rings exhibit positive values as well, resulting conjugation with 18π (4n\u0026thinsp;+\u0026thinsp;2) electrons, satisfying H\u0026uuml;ckel's rule of aromaticity. As directly visualized by the AICD plot of \u003cb\u003e5\u003c/b\u003e, clockwise ring current featuring 18π electrons occurred in double N-annulated perylene subunit, demonstrating N-annulation-induced expansion of the aromatic domain. Accordingly, NICS(1)\u003csub\u003ezz\u003c/sub\u003e value of ring A in \u003cb\u003e9\u003c/b\u003e continually decreases, thus, the aromaticity gains significant strength. Furthermore, AICD plot of \u003cb\u003e9\u003c/b\u003e illustrated clockwise ring current with 34π (4n\u0026thinsp;+\u0026thinsp;2) electrons along the periphery of conjugation system containing the lone pair electrons of six nitrogen atoms, indicating a global aromatic character of this highly crved π-skeleton (Figure S15f). While the hub ring D exhibited weak anticlockwise current, meaning its nonaromatic or anti-aromatic characteristic.\u003c/p\u003e\n\u003ch3\u003eSupramolecular Interactions with Fullerene C\u003c/h3\u003e\n\u003cp\u003eThe electron-rich and curved π-surface of quaterrylene arch should facilitate the concave-convex interactions with electron-deficient fullerene, and the supramolecular behaviors between \u003cb\u003e9\u003c/b\u003e and C\u003csub\u003e60\u003c/sub\u003e were investigated both in solution and solid state. As shown in Figure S7a, the appearance of an isosbestic point in the titration absorption spectrum indicates the formation of a host-guest complex in solution. Further titration experiment of \u003cb\u003e9\u003c/b\u003e with C\u003csub\u003e60\u003c/sub\u003e in toluene solution was conducted by recording the fluorescence intensity changes at 685 and 745 nm. Fluorescence quenching occurred when adding C\u003csub\u003e60\u003c/sub\u003e into solution of \u003cb\u003e9\u003c/b\u003e, indicating efficient energy transfer from \u003cb\u003e9\u003c/b\u003e to C\u003csub\u003e60\u003c/sub\u003e. The titration data analysis supported a 1:1 binding model, and the association constant (\u003cem\u003eK\u003c/em\u003e\u003csub\u003ea\u003c/sub\u003e) was estimated to be 6.97 \u0026times; 10\u003csup\u003e5\u003c/sup\u003e M\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e(Figure S7c), which is larger than perylene bowls and giant molecular bowls.\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e,\u003cspan additionalcitationids=\"CR45 CR46\" citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eThe crystal structure of \u003cb\u003e9@C\u003c/b\u003e\u003csub\u003e\u003cb\u003e60\u003c/b\u003e\u003c/sub\u003e was unambiguously verified by X-ray diffraction, and it revealed 1:1 stoichiometry in line with the observation in solution (Figure S5). In solid state, C\u003csub\u003e60\u003c/sub\u003e and \u003cb\u003e9\u003c/b\u003e reciprocally interact in a complementary concave-convex geometry. Intriguingly, the quaterrylene arch adapts its central angle (\u003cem\u003eθ\u003c/em\u003e) to 120\u0026deg; for optimal contact with C\u003csub\u003e60\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed and \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef), which indicates a peripheral vibration. The closest distance between C\u003csub\u003e60\u003c/sub\u003e and 9 is 3.19 \u0026Aring;, demonstrating the presence of strong π-π interactions (Figure \u003cspan refid=\"MOESM3\" class=\"InternalRef\"\u003eS3\u003c/span\u003ef). Additionally, there exists convex-convex contacts at distances of 3.30 \u0026Aring; to form C\u003csub\u003e60\u003c/sub\u003e and arch arrays along the \u003cem\u003ea\u003c/em\u003e axis (Figure S5). Along the \u003cem\u003ec\u003c/em\u003e axis, \u003cb\u003e9\u003c/b\u003e orientated reversely to form wavy arrays with convex-convex π-π interactions at distances ranging from 3.17 to 3.35 \u0026Aring;. Accordingly, this close-packed long-range ordered stacking might provide multiple channels for effective charge transportation which play an important role in organic electronics devices.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, we present a programmable curved π-extension strategy of structural evolution from a bowl to arches with continuous directional curved topologies, highlighting N-bordered quaterrylene motifs achieved by effective Cadogan reaction as a crucial step. X-ray crystallographic analysis undoubtedly confirms the highly curved arch geometry with positive Gaussian curvature. Moreover, quaterrylene arch demonstrates high arch-to-arch inversion barrier which has been evident from VT \u003csup\u003e1\u003c/sup\u003eH NMR and DFT calculations. Notably, the resultant arch exhibits excellent \u003cem\u003eΦ\u003c/em\u003e\u003csub\u003ef\u003c/sub\u003e up to 79% representing the highest among quaterrylene derivatives. Furthermore, the arch can engage in host-guest complexation with C\u003csub\u003e60\u003c/sub\u003e and co-assembled into tightly associated assemblies. These unique topological rylene-based molecular carbons might provide a potential platform to achieve long-sought-after Vögtle belts. Future work in our laboratory will focus on the functionalization and subsequent “stitching” of these arch units.\u003c/p\u003e \n\n "},{"header":"Methods","content":"\u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003eSynthesis of compound 4\u003c/h2\u003e \u003cp\u003eA 350 mL Schlenk flask was charged with \u003cb\u003e3\u003c/b\u003e (954 mg, 1 mmol), 1,8-dibromo-4,5-di-n-butyl-naphthalenedicarboxylate (1.12 g, 2.3 mmol), Pd\u003csub\u003e2\u003c/sub\u003e(dba)\u003csub\u003e3\u003c/sub\u003e (183 mg, 0.2 mmol), PCy\u003csub\u003e3\u003c/sub\u003e (224 mg, 0.8 mmol), K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e(1.66 g, 12 mmol) and super dry \u003cem\u003eo\u003c/em\u003e-xylene (100 mL) under argon. The mixture was heated to 145 \u003csup\u003eº\u003c/sup\u003eC with vigorous stirring for 36 h. The cooled mixture was purified by column chromatography on silica gel, eluted with CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e/EA = 500:1 then recrystallized through methanol to afford \u003cb\u003e4\u003c/b\u003e as a slate blue solid (740 mg, 55% yield).\u003c/p\u003e \u003c/div\u003e\u003ch2\u003eSynthesis of compound 4\u003c/h2\u003e\u003cp\u003eA 350 mL Schlenk flask was charged with \u003cb\u003e3\u003c/b\u003e (954 mg, 1 mmol), 1,8-dibromo-4,5-di-n-butyl-naphthalenedicarboxylate (1.12 g, 2.3 mmol), Pd\u003csub\u003e2\u003c/sub\u003e(dba)\u003csub\u003e3\u003c/sub\u003e (183 mg, 0.2 mmol), PCy\u003csub\u003e3\u003c/sub\u003e (224 mg, 0.8 mmol), K\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003e3\u003c/sub\u003e(1.66 g, 12 mmol) and super dry \u003cem\u003eo\u003c/em\u003e-xylene (100 mL) under argon. The mixture was heated to 145 \u003csup\u003eº\u003c/sup\u003eC with vigorous stirring for 36 h. The cooled mixture was purified by column chromatography on silica gel, eluted with CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e/EA = 500:1 then recrystallized through methanol to afford \u003cb\u003e4\u003c/b\u003e as a slate blue solid (740 mg, 55% yield).\u003c/p\u003e\u003ch3\u003eSynthesis of compound 6\u003c/h3\u003e\u003cp\u003eA 500 mL flask was charged with \u003cb\u003e4\u003c/b\u003e (820 mg, 0.54 mmol) and dissolved in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e (170 mL), then tert-Butyl nitrite (1.8 mL, 13 mmol) was added. The mixture was stirred at room temperature for 4.5 h. The mixture was purified by flash chromatography on silica gel with CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e then recrystallized through methanol to afford \u003cb\u003e6\u003c/b\u003e as a violet solid (920 mg, 99% yield).\u003c/p\u003e\u003ch2\u003eSynthesis of compound 7\u003c/h2\u003e\u003cp\u003eA 350 mL Schlenk flask was charged with \u003cb\u003e6\u003c/b\u003e (923 mg, 0.6 mmol), PPh\u003csub\u003e3\u003c/sub\u003e (4.43 g, 16.8 mmol) and super dry 1,2-dichlorobenzene (92 mL) under argon. The mixture was stirred at 160 ºC for 12 h. The cooled mixture was purified by column chromatography on silica gel, eluted with CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e/EA = 200:1 then CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e/EA = 50:1, then recrystallized through petroleum ether to afford \u003cb\u003e7\u003c/b\u003e as a brick red solid (440 mg, 60% yield).\u003c/p\u003e\u003ch2\u003eSynthesis of compound 5\u003c/h2\u003e\u003cp\u003eA 100 mL Schlenk flask was charged with \u003cb\u003e4\u003c/b\u003e (326 mg, 0.24 mmol), KOH (337 mg, 6 mmol), and tert-butanol (39 mL) under argon. The mixture was stirred at 85 \u003csup\u003eº\u003c/sup\u003eC for 12 h. After cooling to room temperature, 75mL 1M hydrochloric acid was added at 0 \u003csup\u003eº\u003c/sup\u003eC and stirred for 10 min, then the precipitate was collected by vacuum filtration. 23mL acetic acid was added to the filtrated solid stirring for 3h before 30ml water was added to the mixture, then the precipitate was collected by vacuum filtration to get a purplish gray solid as an intermediate for directly use. A 100 mL Schlenk flask was charged with the intermediate (109 mg, 0.1 mmol), 1-phenylethylamine (103 µL, 0.8 mmol), imidazole (1.8g), and catalytic amount of zinc acetate under argon. The mixture was stirred at 140 \u003csup\u003eº\u003c/sup\u003eC for 12 h. After cooling to room temperature, 5mL 1M hydrochloric acid was added and stirred, then the precipitate was collected by vacuum filtration. The mixture was purified by column chromatography on silica gel, eluted with CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, then recrystallized through methanol to afford \u003cb\u003e5\u003c/b\u003e as a blue-violet solid (90 mg, 70% yield).\u003c/p\u003e\u003ch2\u003eSynthesis of compound 9\u003c/h2\u003e\u003cp\u003eA 100 mL Schlenk flask was charged with \u003cb\u003e8\u003c/b\u003e (244 mg, 0.15 mmol), KOH (427 mg, 7.6 mmol), and tert-butanol (24 mL) under argon. The mixture was stirred at 85 \u003csup\u003eº\u003c/sup\u003eC for 12 h. After cooling to room temperature, 50mL 1M hydrochloric acid was added at 0 \u003csup\u003eº\u003c/sup\u003eC and stirred for 10 min, then the precipitate was collected by vacuum filtration. 15 mL acetic acid was added to the filtrated solid stirring for 3 h before 30 mL water was added to the mixture, and the precipitate was collected by vacuum filtration to get a purplish gray solid as an intermediate for directly use. A 100 mL Schlenk flask was charged with the intermediate (198 mg, 0.145 mmol), 1-phenylethylamine (113 µL, 0.87 mmol), imidazole (3.2 g), and catalytic amount of zinc acetate under argon. The mixture was stirred at 140 \u003csup\u003eº\u003c/sup\u003eC for 12 h. After cooling to room temperature, 10 mL 1M hydrochloric acid was added and stirred, then the precipitate was collected by vacuum filtration. The mixture was purified by column chromatography on silica gel, eluted with petroleum ether/CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e = 1:3, then recrystallized through methanol to afford \u003cb\u003e9\u003c/b\u003e as a purple-gray solid (155 mg, 68% yield).\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCrystallographic data for the structure reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2504268 for \u003cstrong\u003e7\u003c/strong\u003e and CCDC 2504270 for \u003cstrong\u003e9@C60\u003c/strong\u003e. Copies of the data can be obtained free of charge via https://www.ccdc. cam.ac.uk/structures/. The authors declare that the data supporting the findings of this study are available within the paper, the source data and Supplementary Information files. Source data are provided with this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was financially supported by the National Natural Science Foundation of China (No. 22350005 and 22235005). The authors thank Tsinghua Xuetang Talents Program for providing the theoretical calculation resources.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThese authors contributed equally: Kai Chen, Zuoyu Li.\u003c/p\u003e\n\u003cp\u003eAuthors and Affiliations\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eKey Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eKai Chen, Zuoyu Li, Jiangtao Chan, Ming-Wei Wang, Xu Wen, Zixin Liu \u0026amp; Zhaohui Wang\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSchool of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eKai Chen, Wei Jiang\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eKey Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East ChinaUniversity of Science and Technology, Shanghai 200237, China\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eXuan Jin, Guogang Liu\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eZ. W. conceived and supervised the study, and finalized the manuscript. Z. W., W. J., and G. L. participated in scientific discussions and data interpretation. K. C. and Zuoyu Li performed synthetic works. J. C. performed single-crystal X-ray diffraction study. K. C. and X. W. performed physical characterizations. K. C., Zuoyu Li, M. -W. W. and Zixin Liu performed computational studies. X. J. assisted with the scale-up synthesis of compound \u003cstrong\u003e1\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCorresponding authors\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eCorrespondence to Zhaohui Wang,\u0026nbsp;\u003c/p\u003e\n\u003cp\[email protected]\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSupporting information\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eSource Data Fig. 4\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eScholl R, Seer C, Weitzenb\u0026ouml;ck R (1910) Perylen, ein hoch kondensierter aromatischer Kohlenwasserstoff C\u003csub\u003e20\u003c/sub\u003eH\u003csub\u003e12\u003c/sub\u003e. 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Ed.\u003c/em\u003e e202506862\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-8245215/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8245215/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Curved molecular carbons have captured significant concerns due to their distinct properties from planar analogues and topologies serving as segments of diverse nonplanar carbon allotropes. Notably, aromatic ribbons featuring continuously and directionally curved π-surface have been theoretically predicted to be critical to circular carbon analogues, but have remained a synthetic challenge in chemistry. Herein, we address the synthesis and properties of arch-shaped N-bordered nanoribbons which feature rylene backbone attached by five-membered rings at the armchair-edges via a programmable curved π-extension strategy. X-ray crystallographic analyses reveal their directionally and continuously curved π-surfaces with arched topologies and high arch-to-arch inversion barrier according to VT 1H NMR and theoretical calculations. Notably, the resultant quaterrylene arch exhibits a boosted Φf in solution compared to planar quaterrylene diimides and can be associated with C60 in solution and solid state. This work opens a pathway for investigating new series of curved graphene nanoribbons and provides an opportunity for the promising synthesis of relevant long-cherished carbon nanobelts.","manuscriptTitle":"N-Bordered Rylene Arches via Programmable Curved π-Extension","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-09 06:24:52","doi":"10.21203/rs.3.rs-8245215/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"af0807ab-2d4b-48c5-83fd-fdd37c830ded","owner":[],"postedDate":"January 9th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":60762901,"name":"Physical sciences/Chemistry/Organic chemistry/Structure elucidation"},{"id":60762902,"name":"Physical sciences/Chemistry/Physical chemistry"}],"tags":[],"updatedAt":"2026-03-25T14:55:42+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-09 06:24:52","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8245215","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8245215","identity":"rs-8245215","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}