Buckling Cluster-based H-Bonded Icosahedral Capsules and Their Propagation to a Robust Zeolite-like Supramolecular Framework

Buckling Cluster-based H-Bonded Icosahedral Capsules and Their Propagation to a Robust Zeolite-like Supramolecular Framework | 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 Buckling Cluster-based H-Bonded Icosahedral Capsules and Their Propagation to a Robust Zeolite-like Supramolecular Framework Di Sun, Zhan-Hua Zhao, Bao-Liang Han, Haifeng Su, Qi-Lin Guo, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4761254/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 30 Oct, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Hydrogen-bonded assembly of multiple components into well-defined icosahedral capsules akin to virus capsids, has been elusive. In parallel, constructing robust zeolitic-like cluster-based supramolecular frameworks (CSFs) without any coordination bond linkages is challenging. Here, we report the first cluster-based pseudoicosahedral H-bonded capsule Cu60, which is buckled by the self-organization of judiciously designed constituent clusters and anions. The formation of the icosahedron in the solid state takes advantage of 48 charge-assisted CH···F hydrogen bonds between cationic clusters and anions (PF6-), and is highly sensitive to the surface ligands on the clusters with minor structural modification inhibiting its formation. Most excitingly, an extended three-periodic robust zeolitic-like CSF, is inaugurally constructed by edge-sharing the resultant icosahedrons. The perpendicular channels of the CSF feature unusual 3D orthogonal double-helical patterns. The CSF not only keeps its single-crystal character in the desolvated phase, but also exhibits excellent chemical and thermal stabilities as well as long-lived phosphorescence emission. Physical sciences/Chemistry/Supramolecular chemistry Physical sciences/Chemistry/Coordination chemistry Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction Nature is capable of spontaneous association of multiple protein subunits into giant functional superstructures via precise biological self-organization protocol. One accessible and fascinating natural example is a virus capsid―the outer shell of a virus (e.g. the human papillomavirus 1 , Fig. 1A)―comprising many non-covalently linked protein subunits that self-assemble into an icosahedral shell. The icosahedral design by natural systems has myriad advantages, including aesthetic appeal, high stability and storage capacity, as well as minimal information coding requirements. Inspired by this elegant biology, researchers have pursued self-organization through directional noncovalent interactions, such as metal-coordination bonds, to spontaneously fabricate multiple smaller subunits into larger and well-ordered nanoconstructs, toward mimicking viral geometries 2-4 . In this regard, icosahedral coordinative capsules have been achieved, with representative entities like Mo 132 reported by Müller (Fig. 1B) 5 , and Fe 12 reported by Nitschke (Fig. 1C) 6,7 . By contrast, buckling well-defined H-bonded icosahedra is much more challenging, let alone gaining insights into assembled mechanism, in part due to the difficulty in manipulating relatively weak H-bonds compared with coordination bonds. However, rational design protocols regarding icosahedral H-bonded assemblages are significant in that protein-protein interactions described above are mainly formed from many weak interactions including hydrogen bonds. Supramolecular ensembles are recently possible with atom-precise coinage metal (Cu/Ag/Au) clusters as attractive building blocks. Ultrasmall coinage-metal clusters are typically made up of an inorganic metal core and a passivated ligand shell. That the library of protective ligands is extensive affords diverse noncovalent contacts, which directs cluster-cluster assembly to create various well-defined superstructures 8-11 , including helical aggregates 12-15 . Nevertheless, without strong coordination bond linkages 16-19 , assembled cluster-based supramolecular systems are relatively fragile, particularly at high temperature, which has hampered more extensive study of their potential applications. Additionally, programmed assembly of cluster tectons into topologically sophisticated 3D superstructures and/or periodic zeolitic-like crystalline supramolecular networks with tailored properties, as reported in metal-organic frameworks (MOFs) 20-25 , poses a formidable challenge. The main reason comes from the complexity of intercluster interactions, and/or the lack of cluster modules and structure-directing forces. In the present study, we report the first discovery of cluster-based H-bonded pseudoicosahedral capsules Cu 60 (Fig. 1D) formed through the assembly of cationic clusters and anions (PF 6 - ), by means of 48 charge-assisted CH···F hydrogen bonds. The key geometric fragments of the icosahedron can be detected by cold-spray ionization mass spectrometry (CSI-MS), which provides insight into the underlying rules of multicomponent H-bonded assembly. Moreover, each hollow icosahedral capsule is connected to six adjacent equivalent ones by edge-sharing to generate a robust three-periodic zeolitic-like supramolecular architecture, conferring outstanding temperature stability, resistance to acids and bases. The resulting assembled 3D superstructure, referred to as cluster-based supramolecular frameworks (CSFs), will chart a clear approach to guide researchers to control assemblies of stable zeolitic-like cluster-based supramolecular solids without utilizing strong coordination or covalent bonds linkage, and bridges the gap between coinage-metal clusters and hydrogen-bonded organic frameworks (HOFs). Results and discussion Seeking easily accessible construction strategy to create 3D stable crystalline CSFs, our attention was initially captivated by robust HOFs, such as HOF-1 that relies on the H-bonded assembly of organic tectons with tetrahedral geometry to form 3D crystalline networks 26,27 . Taking inspiration from characteristic feature of HOF-1 (Supplementary Fig. 1), we envisioned that harnessing tetrahedrally symmetric clusters as modular building blocks may facilitate building robust CSFs with distinctive topologies and architectures. To this end, we synthesized a copper cluster [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ]PF 6 ( 1 ) (2-mercapto-1-phenylimidazole = H L , and P(C 6 H 4 F) 3 = tris(4-fluorophenyl)phosphine) through reducing the copper salts with NaBH 4 in the presence of H L and P(C 6 H 4 F) 3 under ambient conditions. The structure of 1 was first elucidated by NMR spectroscopy, of which 1 H NMR exhibits a set of shifted ligand signals (Supplementary Fig. 2), verifying the protection of the cluster surface by the mixed ligands. The precise mass and composition of 1 was further confirmed by electrospray ionization mass spectrometry (ESI-MS) in positive mode (Supplementary Fig. 3). The parent cluster ion was found at the most dominant peak, m / z 2283.0142, which could be identified with isotopic envelopes corresponding to [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + ( calc . m / z = 2283.0307). DFT-optimized cluster structure of [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + , characterized as an energy minimum, was found to be of S 4 symmetry (Supplementary Fig. 4), which agrees quite well with the X-ray structure (vide infra). TD-DFT calculated results match well with experimental UV/Vis absorption spectrum of 1 measured in CH 2 Cl 2 , which showed two major UV absorption bands at 358 and 368 nm and a tail up to about 400 nm (Supplementary Fig. 5). Colorless crystals of 1 suitable for X-ray crystallography were obtained by slow vapor diffusion of n -hexane into a concentrated CH 2 Cl 2 solution of the corresponding cluster (PF 6 − salt) at ambient temperature. Microscopic image of the single crystals, exhibited rhombic dodecahedra shape with twelve well-defined diamond facets (Fig. 2 A). Single-crystal X-ray diffraction (SCXRD) analysis revealed that 1 crystallizes in the higher-symmetry cubic crystal system with a non-centrosymmetric space group P —43n (No. 218, Supplementary Table S1 ). Its overall composition contains a cationic cluster [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + , as well as one PF 6 − counterion and interstitial CH 2 Cl 2 molecules. As portrayed in Fig. 2 B, the structural anatomy of [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + could be viewed as a Cu 5 kernel wrapped by peripheral four P(C 6 H 4 F) 3 and four deprotonated L − ligands. The metal core adopts a unique centered tetrahedral geometry. The Cu-Cu bond length in the metal skeleton from the central Cu atom to the vertexes of Cu 4 tetrahedron is equal (2.655(1) Å), suggestive of the presence of significant intramolecular cuprophilic interactions. It is worthy of note that such centered tetrahedral Cu 5 skeleton is very unusual, because a Cambridge Structural Database (CSD) search 28 yields previously reported discrete Cu 5 clusters featuring a planar conformation or a bipyramidal geometry (Fig. 2 C) 29,30 . The center Cu atom is tetrahedrally bonded to all four L − molecules via four Cu-S bonds, while each terminal Cu atom in the Cu 4 tetrahedron is tetrahedrally completed by two µ 3 -S atoms and one N atom from three different L − molecules plus one P atom from one P(C 6 H 4 F) 3 . Thus the entire cationic cluster lies on a special position with S 4 symmetry. Inspection of the rhombic dodecahedral crystal habit in the case of 1 is unexpected among the crystalline forms of coinage metallic clusters, which is evocative of an example of icosahedral viruses crystallized into cubic crystals in a similar dodecahedral shape 31 . These inspire us to conjecture that extraordinary arrangement and packing of cluster tectons might exist. To our delight, the most attractive structural feature of 1 is that twelve copper clusters per unit cell self-assemble into an enclosed pseudoicosahedral capsule denoted as Cu 60 (Fig. 2 D) with approximate diameter of 3.0 nm. The surface of the pseudoicosahedron contains two types of triangular faces (Fig. 2 E- 2 F): 8 equilateral triangles and 12 isosceles triangles, each equilateral triangle with side lengths of 16 Å (the centroid-centroid distances of two adjacent clusters) and each isosceles triangle with side and base lengths of 16 and 13 Å, respectively. Notably, based on ChatGPT prediction 32 , this is the only possible combinatorial outcome for the irregular icosahedron buckled through these triangles and isosceles triangles. The hollow icosahedral capsule Cu 60 could accommodate a sphere with a diameter of about 25 Å, corresponding to a sphere volume of ~ 8177 Å 3 . Our observation of the supramolecular icosahedral assembly that involves the solid-state aggregation of individual clusters is unprecedented and intriguing. More importantly, the atom-precise icosahedral structure will provide much more detailed information for further identifying the origin of this Platonic polyhedral assembly. Figure 2 G shows the electrostatic potential (ESP) mapped onto the electron isodensity surface of [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + . It is found that the surface ESP is highly positive and may be strongly inclined to interact with negatively charged species (i.e., anions) to make supramolecular assemblages. As a result, PF 6 − counterions lie at the centre of equilateral triangles of the icosahedron, wherein half fluoride atoms of each PF 6 − anion interact with three [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + to form a supramolecular trimer. Each copper cluster located in the vertice of icosahedron could be visualized as two parts, a CuP(C 6 H 4 F) 3 and a Cu 3 L 4 (P(C 6 H 4 F) 3 ) 3 moiety, which points inside and outside the surface of icosahedral capsule, respectively. A closer inspection of the intermolecular contact patterns reveals each F atom of the PF 6 − participates in two hydrogen bonds with two fluorobenzenes from two neighboring CuP(C 6 H 4 F) 3 moieties by means of C-H···F charge-assisted hydrogen bonds ( d H···F = 2.56–2.61 Å and θ C−H···F = 127.3°-130.5°). These small H-F separations match well with previous studies of other fluorobenzenes in crystals 33 . In total, the icosahedral capsule is held together by way of 48 CH···F hydrogen bonds. It is especially interesting to note the uniqueness of such cluster-based icosahedral H-bonded capsule Cu 60 is reminiscent of copies of identical protein clusters assembled into icosahedral viral capsids 1 . As mentioned at the outset, supramolecular coordinative icosahedral entities have been identified, such as molybdenum oxide cluster Mo 132 5 and metal-organic capsule Fe 12 6,7 . However, bonding energy for hydrogen bonds (25–40 kJ mol − 1 ) 34,35 is much smaller than those of coordinate covalent bonds (90–350 kJ mol − 1 ) 35 , making well-defined H-bonded icosahedrons more challenging to assembly than their coordination counterparts. From the view of capsule size, the diameter of the supramolecular H-bonding capsule Cu 60 is 3.0 nm, making it comparable to that of the nanosized icosahedral Mo 132 (2.9 nm). To explore the disassembly behavior of the icosahedral nanoconstruct in solution, we carried out CSI-MS characterization, as a variant of ESI-MS operating at low temperature. The CSI-MS was measured by dissolving crystals of 1 in CH 2 Cl 2 , in which the ion source temperature is 0 ºC. Positive-mode CSI-MS affords three sequentially charged ion species (2 + to 4+), centered at m / z 3497.526, 3903.006 and 4711.996, that we attributed to cluster-based H-bonded oligomers, including trimeric {[Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] 3 ·PF 6 } 2+ , pentameric {[Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] 5 ·(PF 6 ) 2 } 3+ , and octameric {[Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] 8 ·(PF 6 ) 4 } 4+ , respectively. The m / z values along with isotopic distribution patterns of each charge state closely match the simulated ones (Fig. 3 ), verifying the assignment. These H-bonded oligomers showcase the increasing cluster aggregations concomitant with the associated increase in anions PF 6 − present which bring discrete clusters together into the oligomers. The optimized H-bonded oligomeric structures (Supplementary Fig. 6) are quite similar to those observed in the crystallographic data. These H-bonded species are considered as geometric fragments of the icosahedral units, which is primarily important to understand the mechanism of formation of the icosahedral capsule from this reaction system. Especially, detection of the most dominant peak of the trimeric {[Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] 3 ·PF 6 } 2+ , is significant, representing the basic trigonal unit of the icosahedron. CSI-MS results indicate that charge-assisted CH···F contacts play a pivotal role in the assembly of clusters with anions into identifiable H-bonded oligomers in solution, prior to crystallization. Fascinatingly, each pseudoicosahedral capsule―considered to be a supramolecular secondary building unit―connects with six other icosahedral capsules through sharing bases of isosceles triangles of the pseudoicosahedron, thereby yielding an extended three-periodic zeolitic-like HOFs (Fig. 4 A), which is the missing link between coinage-metal clusters and HOFs. Of note, topologically, regarding the discrete cluster as a 10-connected node, the whole architecture of the CSF is a unimodal 10-connected framework with the Schläfli symbol (3 16 .4 24 .5 5 ). When viewed in projection down the a axis, the intricate 3D CSF are seen to contain two types of 1D infinite channels (α and β), as illustrated in Fig. 4 B. The α-type channel has cross section of 3.7 Å × 7.2 Å to which the phosphine moieties of clusters are exposed, and guest CH 2 Cl 2 solvents were inside the channel. The β-type channel is formed with phenylimidazole arms of clusters and its channel cross section is 7.0 Å×7.0 Å. Surprisingly, in the tunnel β, the clusters are arranged to form 1D spirals, with four clusters adopting different rotations per spiral of unit cell length. The spirals in turn are intertwined to give the two strands of an infinite double helix with the same right handedness (Fig. 4 C). The helical features of the double helix are defined by a pitch length of 5.2 nm and width of 3.6 nm. The entwined strands are stabilized by charge assisted CH···F H-bonding interactions between the cationic clusters and anions. The tunnels alongside these double helices are filled with disordered CH 2 Cl 2 . The existence of guest molecules CH 2 Cl 2 was also supported by 1 H NMR (Supplementary Fig. 2). It is significant to observe that identical supramolecular double helices are produced along a , b and c -axes, respectively, therefore producing unusual mutually perpendicular double helices in three dimensions (Fig. 4 D). It is worth of noting that it is only recently that 1D double-helical self-assembly has been observed in the realm of coinage metallic clusters aggregates 13–15 , but no example extending into 3D crystallographic axes have appeared until now. Hence, the superstructure of 1 contains another remarkable structural feature of double-stranded helicates which extend in three perpendicular directions, forming 3D orthogonal double-helical patterns, which is advocative of the assembly of double-stranded DNA into various nanostructures in different dimensions 36–38 . Despite the lack of strong metal-coordination bonds, it is the CSF, achieved by charge-assisted hydrogen bonds, that might exhibit improved stability because of the additional electrostatic attraction between the components 39,40 . To confirm the idea, we accessed the chemical durability of crystals of 1 in aqueous solutions with a broad pH range (pH 1–14). After solid 1 was soaked in solutions above-mentioned for three days, there is no obvious difference in morphology and color (Supplementary Fig. 7). Crystals of 1 still retained their single crystallinity, enabling the SCXRD and their unit-cell parameters are almost identical to that of as-synthesized 1 . Moreover, the powder XRD (PXRD) patterns of the sample after prolonged treatment in acidic and basic conditions agree well with the simulated, suggesting that the integrity of the framework is preserved toward both acids and bases (Fig. 5 A). Thermogravimetric analysis (TGA) profile (Fig. 5 B) of freshly prepared crystals 1 showed the first continuous weight loss stepping from room temperature to ~ 170 ºC corresponds to the loss of CH 2 Cl 2 molecules. The superstructure of 1 began to decompose at temperature higher than ~ 215 ºC. To thoroughly understand the thermal stability of the supramolecular framework of 1 , we measured variable-temperature PXRD, which revealed that no phase transition or architecture collapse at elevated temperature range 30–200 ºC (Fig. 5 C). The PXRD results reflect an uncharacteristic robustness of the cluster-based H-bonded assembly even after removal of the solvates from channels, where many other noncovalent coinage-metal cluster-based frameworks would fail. By slowly heating crystals of 1 to 170 ºC under inert atmospheres or in vacuo, 1 could be fully desolvated to obtain CH 2 Cl 2 -free crystals 1-d . The complete removal of guest CH 2 Cl 2 was also confirmed by 1 H NMR spectroscopy (Supplementary Fig. 2), where the chemical shift at 5.25 ppm corresponding to CH 2 Cl 2 disappears completely after activation. The desolvated crystals 1-d exhibited high thermal stability with negligible weight loss occurred until 215 ºC (Fig. 4 B). No significant loss of crystallinity was observed when the CH 2 Cl 2 molecules were removed gently. The resultant crystals 1-d was successfully examined by X-ray crystallographic analysis, explicitly confirming the single-crystal-to-single-crystal transformation. 1-d retained the same P —43n space group as 1 , with a shortening of lattice parameters from 26.1645 Å for ( 1 ) to 25.8013 Å ( 1-d ). The mechanical contraction of the network, with ~ 2% reduction of the initial unit cell volume, occurs without damaging the crystal upon the removal of CH 2 Cl 2 . The atomic resolution of SCXRD allows us to discern subtle variations in the CSF before and after heating. As illustrated in Fig. 3 B, the portal of open channel α′ in 1-d kept almost unchanged as observed in the original channel α in 1 . Closer examination of channel β′ along the a -direction (Fig. 3 C), however, revealed structural subtleties, wherein the chelating arrangement of the imidazole plane restricts its rotation, but a clear rotation of the phenyl group attached to the imidazole moiety partially blocks the portal of the open channel β′, resulting in the shrinkage of the resulted window size (4Å×4Å). CO 2 adsorption-desorption measurement for 1 - d at 273 K showed a fully reversible type-I Langmuir profile (Supplementary Fig. 8), verifying the supramolecular architectural stability and permanent microporous characteristic of 1 - d . It is worth noting that the framework of 1 - d can revert back to its original architecture of 1 when recrystallized from CH 2 Cl 2 , featuring structural dynamism of the CSF. In general, the cluster-cluster interactions can be tailored via modification of the ligand shell. For 1 , due to the inductive effect associated with fluorine atom at the para -position of benzene, the positively polarized surfaces of the fluorinated aromatics are prone to interact with electron-rich anions. We reasoned that substitution of the para -F atom with H may be expected to disrupt CH···F hydrogen bonds, further markedly affecting the structure of the resulting CSFs. To verify this, we tried to synthesize another analog [Cu 5 L 4 (PPh 3 ) 4 ]PF 6 ( 2 ), by replacing P(C 6 H 4 F) 3 with triphenylphosphine (PPh 3 ). X-ray diffraction analysis at 173 K for single crystal of 2 established that it occurs in the centrosymmetric tetrahedral space group P 4/ ncc (No. 130, Supplementary Table S2) with the composition of [Cu 5 L 4 (PPh 3 ) 4 ]PF 6 ·CH 2 Cl 2 , proved by ESI-MS (Supplementary Fig. 9). As anticipated, the cationic cluster [Cu 5 L 4 (PPh 3 ) 4 ] + is isostructural with [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + . In comparison with 1 , however, SCXRD revealed that 2 exhibits distinctly different assembly behavior, whereby [Cu 5 L 4 (PPh 3 ) 4 ] + clusters spontaneously organize into another 3D CSF. The topology of 2 can be described as a compressed pcu (primitive cubic) net with nodes as [Cu 5 L 4 (PPh 3 ) 4 ] + clusters. The basic repeating unit of the 3D CSF contains a double cubane-like cage fused by two same compressed cubic supramolecular cages (Fig. 6 A), of which each is formed by eight clusters through weak tecton-tecton contacts (i.e., CH···π and H···H interactions) (Supplementary Fig. 10). Interestingly, self-assembled hexafluorophosphate-dichloromethane anionic clusters of [PF 6 •(CH 2 Cl 2 ) 4 ] − are docked in the confined cavities of the double cubane-like cage, respectively. Structural characterization reveals that PF 6 − anion in the [PF 6 •(CH 2 Cl 2 ) 4 ] − only uses one fluoride atom as quadruple H-bond acceptors to bond with four CH 2 Cl 2 molecules as single H-bond donor, thereby resulting in four weak nonconventional C-H···F hydrogen bonds ( d H···F = 2.58 Å and θ C−H···F = 144°). Strikingly, [PF 6 •(CH 2 Cl 2 ) 4 ] − has a C 4 symmetry with a 4-fold axis passing through F-P-F of PF 6 − , thus producing two equivalent enantiomers, R -[PF 6 •(CH 2 Cl 2 ) 4 ] − and S -[PF 6 •(CH 2 Cl 2 ) 4 ] − (Fig. 6 B). Notably, this is the first structural evidence on chiral PF 6 − -CH 2 Cl 2 solvated anionic clusters imprisoned in the cage. The calculated independent gradient model based on Hirshfeld partition (IGMH) analysis on the supramolecular species [Cu 5 L 4 (P(C 6 H 4 F) 3 ) 4 ] + •PF 6 − indicates the apparent strong CH···F interactions in the green section occur between C-H groups of the fluorobenzene rings and F atoms from PF 6 − anion (Fig. 6 C), which is crucial for the enhanced stability of the rigid supramolecular framework in 1 . In contrast, 2 does not form the target [Cu 5 L 4 (PPh 3 ) 4 ] + •PF 6 − due to negligible weak CH···F interactions between PF 6 − and phenyl ring (Fig. 6 C). On the contrary, the PF 6 − in 2 has a high tendency to be solvated by CH 2 Cl 2 molecules, leading to the formation of solvated anions as discussed above. With the above considerations in mind, we surmised that the absence of strong charge-assisted CH···F H-bonding interactions in 2 will make the CSF more labile. As anticipated, the crystals 2 are extremely fragile, quickly cracked and lost their crystallinity after being taken out of the mother liquor. Solid-state UV/Vis diffuse-reflectance spectroscopy of the crystalline sample of 1 displayed that it is transparent in the visible region of 400–800 nm (Fig. 6 D). We investigated the steady-state photoluminescence (PL) spectrum of 1 at room temperature, which presented a weak green emission band at around 547 nm upon excitation at 365 nm, with a large Stokes shift (~ 182 nm). Additionally, the temperature-dependent PL emission was also measured from 300 to 80 K (Fig. 6 D). The PL spectrum blue-shifted with decreasing temperature from 547 nm at 300 K to 507 nm at 80 K. The corresponding PL intensity enhanced nearly 11-fold. The increased PL intensity upon cooling is a typical phosphorescence characteristic owing to the effective reduction of nonradiative decay at low temperature, whereas the 40-nm hypsochromic-shifted emission may be caused by the restriction of the rotation of the phenyl group attached to the imidazole moiety at low temperature. The emission decay curve monitored at 547 nm gave relatively long lifetimes of 13–16 ms at 80–170 K (Supplementary Table S3), which is even visible to the naked eye (inset of Fig. 6 D). Both long emission lifetime (millisecond) and large Stokes shift in 1 suggest the phosphorescence nature of the green luminescence, primarily originating from a process involved ligand to metal charge transfer (LMCT) or ligand-to-metal-metal charge transfer (LMMCT) 41–43 . Conclusion In conclusion, the results presented here demonstrate for the first time the icosahedral H-bonded nanocapsules assembled from individual clusters. These capsules propagate through edge-sharing into a novel 3D zeolitic-like CSF, offering distinct advantages of being both excellently chemically and thermally stabile. This intrinsic stability can be ascribed to the multiple remarkable charge-assisted CH···F hydrogen bonds. This wholly cluster-based H-bonding framework expands the scope of complicated cluster-based supramolecular architectures, and bridges the gap between clusters and HOFs. We expect that this finding can inspire future exploration of the uncovering completely new zeolitic-like CSFs, which may in turn find applications in, for example, gas storage, separation processes, and catalysis. Methods Synthesis of 1. In total, 3 ml CH 2 Cl 2 /CH 3 OH (v:v = 2:1) mixture of copper(II) trifluoroacetate hydrate (43 mg) and tetrabutylammonium hexafluorophosphate (10 mg) were stirred for 10 min. Then P(C 6 H 4 F) 3 (63 mg) and 2-mercapto-1-phenylimidazole (35 mg) were added. With stirring for 15 min, 20 mg NaBH 4 in 1 ml H 2 O, was then added dropwise, which produced a bright red solution. The mixture was stirred for 6h and being aged at 4°C for 12 h. Next, the aqueous phase was removed and the obtained organic phase was washed with H 2 O several times. The resulted solution was centrifuged for 3 min at 10000 r min -1 and the red-brown solution was filtered. The solution was subjected to diffusion of hexane at room temperature. Colorless crystals were obtained after three days (20% yield, based on Cu). Synthesis of 2. 2 was synthesized by a similar procedure with 1 , except the PPh 3 instead of P(C 6 H 4 F) 3 . Colorless crystals were obtained after four days (15% yield, based on Cu). Declarations Additional information Supplementary information is linked to the online version of this paper at http://www.nature.com/ . Competing interests The authors declare no competing interests. Author contributions G.G.L. and D.S. conceived and designed the experiments; Z.H.Z., B.L.H. and H.F.S. conducted synthesis and characterization; Z.H.Z., B.L.H., Q.L.G. and W.X.W. researched and analyzed data; J.Q.Z., Y.N.G., J.L.L. and P.C. contributed to scientific discussion; Z.H.Z., B.L.H., G.G.L. and D.S. wrote, reviewed and edited the paper. All authors discussed the results and commented on the manuscript. Acknowledgement This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 91961105, 21641011, 21822107, 21801212), the Natural Science Foundation of Fujian Province (Nos. 2022J01298), the Taishan Scholar Project of Shandong Province of China (Nos. tsqn201812003 and ts20190908), the Natural Science Foundation of Shandong Province (No. ZR2019ZD45, JQ201803 and ZR2017MB061). Data availability. The X-ray crystallographic coordinates for structures reported in this article have been deposited at the Cambridge Crystal-lographic Data Centre, under deposition number CCDC: 2366513 for 1 , 2366514 for 1-d , 2366515 for 2 . The data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif . References Singharoy A et al (2013) Epitope fluctuations in the human papillomavirus are under dynamic allosteric control: a computational evaluation of a new vaccine design strategy. J Am Chem Soc 135:18458–18468 Xu N, Gan H-M, Qin C, Wang X-L, Su Z-M (2019) From octahedral to icosahedral metal-organic polyhedra assembled from two types of polyoxovanadate clusters. Angew Chem Int Ed 58:4649–4653 Atwood JL et al (2004) Toward mimicking viral geometry with metal-organic systems. 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Chem Rev 115:7589–7728 Zheng J, Lu Z, Wu K, Ning GH, Li D (2020) Coinage-metal-based cyclic trinuclear complexes with metal–metal interactions: theories to experiments and structures to functions. Chem Rev 120:9675–9742 Kang X, Zhu M (2019) Tailoring the photoluminescence of atomically precise nanoclusters. Chem Soc Rev 48:2422–2457 Additional Declarations There is NO Competing Interest. Supplementary Files SIV6.docx Cite Share Download PDF Status: Published Journal Publication published 30 Oct, 2024 Read the published version in Nature Communications → 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. 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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-4761254","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":335371959,"identity":"cf3ef05d-46f8-44b0-b1ae-82b61beb9ee4","order_by":0,"name":"Di Sun","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAArUlEQVRIiWNgGAWjYDCCA0D8gYEZxDQgXgvjDJK1MPOQpIXv/BmzxzZ/rBMb2Ju3STDU3CGsRfJGjrlxblt6YgPPsTIJhmPPCGsxuMFjJp3bcDixQSLHTIKx4TARWoAOk7b4A9Qi/4ZYLQdyzKQZ2EC28BCpRfJGWplkb1u6cRtPWrFFwjEitPCdP7xN4scfa9l+9sMbb3yoIUILHLCBiAQSNIyCUTAKRsEowAMAbCM3QArJnbUAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0001-5966-1207","institution":"Shandong University","correspondingAuthor":true,"prefix":"","firstName":"Di","middleName":"","lastName":"Sun","suffix":""},{"id":335371960,"identity":"a8a0de0b-482f-40e4-97cc-81f5e5f0227c","order_by":1,"name":"Zhan-Hua Zhao","email":"","orcid":"","institution":"Huaqiao University","correspondingAuthor":false,"prefix":"","firstName":"Zhan-Hua","middleName":"","lastName":"Zhao","suffix":""},{"id":335371961,"identity":"616e7f70-7fab-4801-936e-6bc4d36d8e06","order_by":2,"name":"Bao-Liang Han","email":"","orcid":"https://orcid.org/0000-0002-4601-2600","institution":"Shandong University","correspondingAuthor":false,"prefix":"","firstName":"Bao-Liang","middleName":"","lastName":"Han","suffix":""},{"id":335371962,"identity":"d196330e-54c1-46f2-971d-edcdfebd25cd","order_by":3,"name":"Haifeng Su","email":"","orcid":"","institution":"State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Haifeng","middleName":"","lastName":"Su","suffix":""},{"id":335371963,"identity":"0986f23b-771c-4cce-ba25-d76668827f27","order_by":4,"name":"Qi-Lin Guo","email":"","orcid":"","institution":"Huaqiao University","correspondingAuthor":false,"prefix":"","firstName":"Qi-Lin","middleName":"","lastName":"Guo","suffix":""},{"id":335371964,"identity":"1eed771a-deba-4473-9574-84da22c67983","order_by":5,"name":"Wen-Xin Wang","email":"","orcid":"","institution":"Shandong University","correspondingAuthor":false,"prefix":"","firstName":"Wen-Xin","middleName":"","lastName":"Wang","suffix":""},{"id":335371965,"identity":"cbe935a1-0640-4212-91e4-476598bc38fe","order_by":6,"name":"Jing-Qiu Zhuo","email":"","orcid":"","institution":"Huaqiao University","correspondingAuthor":false,"prefix":"","firstName":"Jing-Qiu","middleName":"","lastName":"Zhuo","suffix":""},{"id":335371966,"identity":"4e83af51-f072-47c8-8205-d3e9025abcea","order_by":7,"name":"Yong-Nan Guo","email":"","orcid":"","institution":"Huaqiao University","correspondingAuthor":false,"prefix":"","firstName":"Yong-Nan","middleName":"","lastName":"Guo","suffix":""},{"id":335371967,"identity":"5704482d-de62-4c80-adaf-322807e44d7f","order_by":8,"name":"Jia-Long Liu","email":"","orcid":"","institution":"Huaqiao University","correspondingAuthor":false,"prefix":"","firstName":"Jia-Long","middleName":"","lastName":"Liu","suffix":""},{"id":335371968,"identity":"60f4e1de-ada8-4090-9ae2-a7d505f284c4","order_by":9,"name":"Geng-Geng Luo","email":"","orcid":"","institution":"Huaqiao University","correspondingAuthor":false,"prefix":"","firstName":"Geng-Geng","middleName":"","lastName":"Luo","suffix":""},{"id":335371969,"identity":"3e753753-c20e-4e13-b978-aa627e1e49ab","order_by":10,"name":"Ping Cui","email":"","orcid":"","institution":"Shandong University","correspondingAuthor":false,"prefix":"","firstName":"Ping","middleName":"","lastName":"Cui","suffix":""}],"badges":[],"createdAt":"2024-07-18 09:01:14","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4761254/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4761254/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-024-53640-4","type":"published","date":"2024-10-30T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":61820070,"identity":"c01f6349-fe70-418b-8bc9-38c952388c90","added_by":"auto","created_at":"2024-08-06 01:35:35","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":469735,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSupramolecular icosahedral entities.\u003c/strong\u003e \u003cstrong\u003eA\u003c/strong\u003e, The human papillomavirus. Reprinted with permission from reference\u003csup\u003e1\u003c/sup\u003e. Copyright 2013, American Chemical Society. \u003cstrong\u003eB\u003c/strong\u003e, Molybdenum oxide cluster Mo\u003csub\u003e132\u003c/sub\u003e. \u003cstrong\u003eC\u003c/strong\u003e, Metal-organic capsule Fe\u003csub\u003e12\u003c/sub\u003e. \u003cstrong\u003eD\u003c/strong\u003e, Cluster-based H-bonded capsule Cu\u003csub\u003e60\u003c/sub\u003e reported in this work.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/8b6d90f44d06868ba1d06de6.png"},{"id":61820072,"identity":"00511600-d9a6-4f0c-a155-83f9253b891e","added_by":"auto","created_at":"2024-08-06 01:35:35","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":642650,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eA\u003c/strong\u003e, Dodecahedral rhombohedral crystal habit of \u003cstrong\u003e1\u003c/strong\u003e, as observed by polarization microscope. \u003cstrong\u003eB\u003c/strong\u003e, X-ray crystal structure of [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e. Color code: gray, C; blue, N; orange, P; green, Cl; turquoise, Cu. \u003cstrong\u003eC\u003c/strong\u003e, Reported Cu\u003csub\u003e5\u003c/sub\u003e core with a planar conformation or a bipyramidal geometry. \u003cstrong\u003eD\u003c/strong\u003e, Arrangement of twelve clusters at the vertexes of the pseudoicosahedron. \u003cstrong\u003eE\u003c/strong\u003e and \u003cstrong\u003eF\u003c/strong\u003e: schematic representation of the pseudoicosahedron and its expansion surface. \u003cstrong\u003eG\u003c/strong\u003e, Electronstatic potential (ESP) diagram of [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/35668ca67122c676a21bb90c.png"},{"id":61820497,"identity":"5144342b-3af1-4933-98a3-d32386de8569","added_by":"auto","created_at":"2024-08-06 01:43:35","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":305820,"visible":true,"origin":"","legend":"\u003cp\u003eComparison of the experimental and simulated isotopic envelopes for H-bonded oligomers identified within the CSI-MS spectra of \u003cstrong\u003e1\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/dd119675fb8525b847747631.png"},{"id":61820074,"identity":"0ef51992-5c51-40aa-ace4-25879d8fbc21","added_by":"auto","created_at":"2024-08-06 01:35:35","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1180244,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eA\u003c/strong\u003e, 0D pseudo-icosahedron capsule and edge-sharing pseudo-icosahedron stacking for the formation of 3D structure. \u003cstrong\u003eB\u003c/strong\u003e, Single-crystal-to-single-crystal structure transformation between\u003cstrong\u003e \u003c/strong\u003ecrystals\u003cstrong\u003e 1 \u003c/strong\u003eand \u003cstrong\u003e1-d\u003c/strong\u003e by heating activation. \u003cstrong\u003eC\u003c/strong\u003e, Double-helix with each helix distinguished by red- or blue clusters. Inset: overlay of crystal structures of [Cu\u003csub\u003e5\u003c/sub\u003eL\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e in \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e1\u003c/strong\u003e-\u003cstrong\u003ed\u003c/strong\u003e. \u003cstrong\u003eD\u003c/strong\u003e, Schematic 3D orthogonal double-helical patterns.\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/88c52cdc7acad75e0cb078bf.png"},{"id":61820071,"identity":"dc1f4e18-1fbc-4b45-b429-f525669ffffc","added_by":"auto","created_at":"2024-08-06 01:35:35","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":111556,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eA\u003c/strong\u003e, PXRD of \u003cstrong\u003e1\u003c/strong\u003e in aqueous solution with a broad pH range (1-14). \u003cstrong\u003eB\u003c/strong\u003e, TGA of crystals \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e1\u003c/strong\u003e-\u003cstrong\u003ed\u003c/strong\u003e. \u003cstrong\u003eC\u003c/strong\u003e, Variable-temperature PXRD of \u003cstrong\u003e1\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/389519e8bc0debe85762fb26.png"},{"id":61820075,"identity":"20afdc1f-c3d7-424a-b9b2-db525a637397","added_by":"auto","created_at":"2024-08-06 01:35:35","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":455698,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eA\u003c/strong\u003e, the compressed\u003cstrong\u003e pcu\u003c/strong\u003e net constructed from double cubane-like cages. \u003cstrong\u003eB\u003c/strong\u003e, A couple of equivalent enantiomers, R-[PF\u003csub\u003e6\u003c/sub\u003e•(CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e-\u003c/sup\u003e and S-[PF\u003csub\u003e6\u003c/sub\u003e•(CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e-\u003c/sup\u003e. \u003cstrong\u003eC\u003c/strong\u003e, noncovalent interactions analysis of [Cu\u003csub\u003e5\u003c/sub\u003eL\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e•PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e and [Cu\u003csub\u003e5\u003c/sub\u003eL\u003csub\u003e4\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e•PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e. \u003cstrong\u003eD\u003c/strong\u003e, UV/vis DRS and temperature-dependent PL spectra of \u003cstrong\u003e1\u003c/strong\u003e. Inset: photographs were taken under a 365 nm UV lamp on and off (100 ms) at 80 K.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/a62dcf6b2ad2aca6842b3c6a.png"},{"id":67918328,"identity":"a25c9e36-7736-4772-8417-2bd37368f657","added_by":"auto","created_at":"2024-10-31 07:05:37","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4205890,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/0ab2686f-c92a-459c-bdc6-3e7b7e2368fb.pdf"},{"id":61820076,"identity":"c4c262dd-ab02-48a1-801d-2ae57c9be002","added_by":"auto","created_at":"2024-08-06 01:35:35","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":4383013,"visible":true,"origin":"","legend":"","description":"","filename":"SIV6.docx","url":"https://assets-eu.researchsquare.com/files/rs-4761254/v1/be2274181e79d4d71f96b895.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Buckling Cluster-based H-Bonded Icosahedral Capsules and Their Propagation to a Robust Zeolite-like Supramolecular Framework","fulltext":[{"header":"Introduction","content":"\u003cp\u003eNature\u0026nbsp;is capable of spontaneous association of multiple protein subunits into giant functional superstructures via precise biological self-organization protocol. One accessible and fascinating natural example is a virus capsid―the outer shell of a virus (e.g. the human papillomavirus\u003csup\u003e1\u003c/sup\u003e,\u0026nbsp;Fig. 1A)―comprising many non-covalently linked protein subunits that self-assemble into an icosahedral shell. The icosahedral design by natural systems has myriad advantages, including aesthetic appeal, high stability and storage capacity, as well as minimal information coding requirements. Inspired by this elegant biology, researchers have pursued self-organization through directional noncovalent interactions, such as metal-coordination bonds, to spontaneously fabricate multiple smaller subunits into larger and well-ordered nanoconstructs, toward mimicking viral geometries\u003csup\u003e2-4\u003c/sup\u003e. In this regard, icosahedral coordinative capsules have been achieved, with representative entities like Mo\u003csub\u003e132\u003c/sub\u003e reported by M\u0026uuml;ller (Fig. 1B)\u003csup\u003e5\u003c/sup\u003e, and Fe\u003csub\u003e12\u003c/sub\u003e reported by Nitschke (Fig. 1C)\u003csup\u003e6,7\u003c/sup\u003e. By contrast, buckling well-defined H-bonded icosahedra is much more challenging, let alone gaining insights into assembled mechanism, in part due to the difficulty in manipulating relatively weak H-bonds compared with coordination bonds. However, rational design protocols regarding icosahedral H-bonded assemblages are significant in that protein-protein interactions described above are mainly formed from many weak interactions including hydrogen bonds.\u003c/p\u003e\n\u003cp\u003eSupramolecular ensembles are recently possible with atom-precise coinage metal (Cu/Ag/Au) clusters as attractive building blocks. Ultrasmall coinage-metal clusters are typically made up of an inorganic metal core and a passivated ligand shell. That the library of protective ligands is extensive affords diverse noncovalent contacts, which directs cluster-cluster assembly to create various well-defined superstructures\u003csup\u003e8-11\u003c/sup\u003e, including helical aggregates\u003csup\u003e12-15\u003c/sup\u003e. Nevertheless, without strong coordination bond linkages\u003csup\u003e16-19\u003c/sup\u003e, assembled cluster-based supramolecular systems are relatively fragile, particularly at high temperature, which has hampered more extensive study of their potential applications. Additionally, programmed\u0026nbsp;assembly of cluster tectons into topologically sophisticated 3D superstructures and/or periodic zeolitic-like crystalline supramolecular networks with tailored properties, as reported in metal-organic frameworks (MOFs)\u003csup\u003e20-25\u003c/sup\u003e, poses a formidable challenge. The main reason comes from the complexity of intercluster interactions, and/or the lack of cluster modules and structure-directing forces.\u003c/p\u003e\n\u003cp\u003eIn the present study, we report the first discovery of cluster-based H-bonded pseudoicosahedral capsules Cu\u003csub\u003e60\u003c/sub\u003e (Fig. 1D) formed through the assembly of cationic clusters and anions (PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e-\u003c/sup\u003e), by means of 48 charge-assisted CH\u0026middot;\u0026middot;\u0026middot;F hydrogen bonds. The key\u0026nbsp;geometric fragments\u0026nbsp;of the icosahedron can be detected by\u0026nbsp;cold-spray ionization mass spectrometry (CSI-MS), which provides insight into the underlying rules of multicomponent H-bonded assembly. Moreover, each hollow icosahedral capsule is connected to six adjacent equivalent ones by edge-sharing to generate a robust\u0026nbsp;three-periodic\u0026nbsp;zeolitic-like supramolecular architecture, conferring outstanding temperature stability, resistance to acids and bases. The resulting assembled 3D superstructure, referred to as cluster-based supramolecular frameworks (CSFs), will chart a clear approach to guide researchers to control assemblies of stable\u0026nbsp;zeolitic-like\u0026nbsp;cluster-based supramolecular solids without utilizing strong coordination or covalent bonds linkage, and bridges the gap between coinage-metal clusters and hydrogen-bonded organic frameworks\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e(HOFs).\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003eSeeking easily accessible construction strategy to create 3D stable crystalline CSFs, our attention was initially captivated by robust HOFs, such as HOF-1 that relies on the H-bonded assembly of organic tectons with tetrahedral geometry to form 3D crystalline networks\u003csup\u003e26,27\u003c/sup\u003e. Taking inspiration from characteristic feature of HOF-1 (Supplementary Fig.\u0026nbsp;1), we envisioned that harnessing tetrahedrally symmetric clusters as modular building blocks may facilitate building robust CSFs with distinctive topologies and architectures. To this end, we synthesized a copper cluster [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]PF\u003csub\u003e6\u003c/sub\u003e (\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e) (2-mercapto-1-phenylimidazole\u0026thinsp;=\u0026thinsp;H\u003cem\u003eL\u003c/em\u003e, and P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e = tris(4-fluorophenyl)phosphine) through reducing the copper salts with NaBH\u003csub\u003e4\u003c/sub\u003e in the presence of H\u003cem\u003eL\u003c/em\u003e and P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e under ambient conditions. The structure of \u003cb\u003e1\u003c/b\u003e was first elucidated by NMR spectroscopy, of which \u003csup\u003e1\u003c/sup\u003eH NMR exhibits a set of shifted ligand signals (Supplementary Fig.\u0026nbsp;2), verifying the protection of the cluster surface by the mixed ligands. The precise mass and composition of \u003cb\u003e1\u003c/b\u003e was further confirmed by electrospray ionization mass spectrometry (ESI-MS) in positive mode (Supplementary Fig.\u0026nbsp;3). The parent cluster ion was found at the most dominant peak, \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e 2283.0142, which could be identified with isotopic envelopes corresponding to [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e (\u003cem\u003ecalc\u003c/em\u003e. \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2283.0307). DFT-optimized cluster structure of [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e, characterized as an energy minimum, was found to be of \u003cem\u003eS\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e symmetry (Supplementary Fig.\u0026nbsp;4), which agrees quite well with the X-ray structure (vide infra). TD-DFT calculated results match well with experimental UV/Vis absorption spectrum of \u003cb\u003e1\u003c/b\u003e measured in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, which showed two major UV absorption bands at 358 and 368 nm and a tail up to about 400 nm (Supplementary Fig.\u0026nbsp;5).\u003c/p\u003e \u003cp\u003eColorless crystals of \u003cb\u003e1\u003c/b\u003e suitable for X-ray crystallography were obtained by slow vapor diffusion of \u003cem\u003en\u003c/em\u003e-hexane into a concentrated CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solution of the corresponding cluster (PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e salt) at ambient temperature. Microscopic image of the single crystals, exhibited rhombic dodecahedra shape with twelve well-defined diamond facets (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA). Single-crystal X-ray diffraction (SCXRD) analysis revealed that \u003cb\u003e1\u003c/b\u003e crystallizes in the higher-symmetry cubic crystal system with a non-centrosymmetric space group \u003cem\u003eP\u003c/em\u003e\u0026mdash;43n (No. 218, Supplementary Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). Its overall composition contains a cationic cluster [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e, as well as one PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e counterion and interstitial CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e molecules. As portrayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eB, the structural anatomy of [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e could be viewed as a Cu\u003csub\u003e5\u003c/sub\u003e kernel wrapped by peripheral four P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e and four deprotonated \u003cem\u003eL\u003c/em\u003e\u003csup\u003e\u003cem\u003e\u0026minus;\u003c/em\u003e\u003c/sup\u003e ligands. The metal core adopts a unique centered tetrahedral geometry. The Cu-Cu bond length in the metal skeleton from the central Cu atom to the vertexes of Cu\u003csub\u003e4\u003c/sub\u003e tetrahedron is equal (2.655(1) \u0026Aring;), suggestive of the presence of significant intramolecular cuprophilic interactions. It is worthy of note that such centered tetrahedral Cu\u003csub\u003e5\u003c/sub\u003e skeleton is very unusual, because a Cambridge Structural Database (CSD) search\u003csup\u003e28\u003c/sup\u003e yields previously reported discrete Cu\u003csub\u003e5\u003c/sub\u003e clusters featuring a planar conformation or a bipyramidal geometry (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC)\u003csup\u003e29,30\u003c/sup\u003e. The center Cu atom is tetrahedrally bonded to all four \u003cem\u003eL\u003c/em\u003e\u003csup\u003e\u003cem\u003e\u0026minus;\u003c/em\u003e\u003c/sup\u003e molecules via four Cu-S bonds, while each terminal Cu atom in the Cu\u003csub\u003e4\u003c/sub\u003e tetrahedron is tetrahedrally completed by two \u003cem\u003e\u0026micro;\u003c/em\u003e\u003csub\u003e3\u003c/sub\u003e-S atoms and one N atom from three different \u003cem\u003eL\u003c/em\u003e\u003csup\u003e\u003cem\u003e\u0026minus;\u003c/em\u003e\u003c/sup\u003e molecules plus one P atom from one P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e. Thus the entire cationic cluster lies on a special position with \u003cem\u003eS\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e symmetry.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eInspection of the rhombic dodecahedral crystal habit in the case of \u003cb\u003e1\u003c/b\u003e is unexpected among the crystalline forms of coinage metallic clusters, which is evocative of an example of icosahedral viruses crystallized into cubic crystals in a similar dodecahedral shape\u003csup\u003e31\u003c/sup\u003e. These inspire us to conjecture that extraordinary arrangement and packing of cluster tectons might exist. To our delight, the most attractive structural feature of \u003cb\u003e1\u003c/b\u003e is that twelve copper clusters per unit cell self-assemble into an enclosed pseudoicosahedral capsule denoted as Cu\u003csub\u003e60\u003c/sub\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eD) with approximate diameter of 3.0 nm. The surface of the pseudoicosahedron contains two types of triangular faces (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eE-\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eF): 8 equilateral triangles and 12 isosceles triangles, each equilateral triangle with side lengths of 16 \u0026Aring; (the centroid-centroid distances of two adjacent clusters) and each isosceles triangle with side and base lengths of 16 and 13 \u0026Aring;, respectively. Notably, based on ChatGPT prediction\u003csup\u003e32\u003c/sup\u003e, this is the only possible combinatorial outcome for the irregular icosahedron buckled through these triangles and isosceles triangles. The hollow icosahedral capsule Cu\u003csub\u003e60\u003c/sub\u003e could accommodate a sphere with a diameter of about 25 \u0026Aring;, corresponding to a sphere volume of ~\u0026thinsp;8177 \u0026Aring;\u003csup\u003e3\u003c/sup\u003e. Our observation of the supramolecular icosahedral assembly that involves the solid-state aggregation of individual clusters is unprecedented and intriguing. More importantly, the atom-precise icosahedral structure will provide much more detailed information for further identifying the origin of this Platonic polyhedral assembly.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eG shows the electrostatic potential (ESP) mapped onto the electron isodensity surface of [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e. It is found that the surface ESP is highly positive and may be strongly inclined to interact with negatively charged species (i.e., anions) to make supramolecular assemblages. As a result, PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e counterions lie at the centre of equilateral triangles of the icosahedron, wherein half fluoride atoms of each PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e anion interact with three [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e to form a supramolecular trimer. Each copper cluster located in the vertice of icosahedron could be visualized as two parts, a CuP(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e and a Cu\u003csub\u003e3\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e moiety, which points inside and outside the surface of icosahedral capsule, respectively. A closer inspection of the intermolecular contact patterns reveals each F atom of the PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e participates in two hydrogen bonds with two fluorobenzenes from two neighboring CuP(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e moieties by means of C-H\u0026middot;\u0026middot;\u0026middot;F charge-assisted hydrogen bonds (\u003cem\u003ed\u003c/em\u003e\u003csub\u003eH\u0026middot;\u0026middot;\u0026middot;F\u003c/sub\u003e = 2.56\u0026ndash;2.61 \u0026Aring; and \u003cem\u003eθ\u003c/em\u003e\u003csub\u003eC\u0026minus;H\u0026middot;\u0026middot;\u0026middot;F\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;127.3\u0026deg;-130.5\u0026deg;). These small H-F separations match well with previous studies of other fluorobenzenes in crystals\u003csup\u003e33\u003c/sup\u003e. In total, the icosahedral capsule is held together by way of 48 CH\u0026middot;\u0026middot;\u0026middot;F hydrogen bonds. It is especially interesting to note the uniqueness of such cluster-based icosahedral H-bonded capsule Cu\u003csub\u003e60\u003c/sub\u003e is reminiscent of copies of identical protein clusters assembled into icosahedral viral capsids\u003csup\u003e1\u003c/sup\u003e. As mentioned at the outset, supramolecular coordinative icosahedral entities have been identified, such as molybdenum oxide cluster Mo\u003csub\u003e132\u003c/sub\u003e\u003csup\u003e5\u003c/sup\u003e and metal-organic capsule Fe\u003csub\u003e12\u003c/sub\u003e\u003csup\u003e6,7\u003c/sup\u003e. However, bonding energy for hydrogen bonds (25\u0026ndash;40 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003csup\u003e34,35\u003c/sup\u003e is much smaller than those of coordinate covalent bonds (90\u0026ndash;350 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003csup\u003e35\u003c/sup\u003e, making well-defined H-bonded icosahedrons more challenging to assembly than their coordination counterparts. From the view of capsule size, the diameter of the supramolecular H-bonding capsule Cu\u003csub\u003e60\u003c/sub\u003e is 3.0 nm, making it comparable to that of the nanosized icosahedral Mo\u003csub\u003e132\u003c/sub\u003e (2.9 nm).\u003c/p\u003e \u003cp\u003eTo explore the disassembly behavior of the icosahedral nanoconstruct in solution, we carried out CSI-MS characterization, as a variant of ESI-MS operating at low temperature. The CSI-MS was measured by dissolving crystals of \u003cb\u003e1\u003c/b\u003e in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, in which the ion source temperature is 0 \u0026ordm;C. Positive-mode CSI-MS affords three sequentially charged ion species (2\u0026thinsp;+\u0026thinsp;to 4+), centered at \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e 3497.526, 3903.006 and 4711.996, that we attributed to cluster-based H-bonded oligomers, including trimeric {[Cu\u003csub\u003e5\u003c/sub\u003eL\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csub\u003e3\u003c/sub\u003e\u0026middot;PF\u003csub\u003e6\u003c/sub\u003e}\u003csup\u003e2+\u003c/sup\u003e, pentameric {[Cu\u003csub\u003e5\u003c/sub\u003eL\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csub\u003e5\u003c/sub\u003e\u0026middot;(PF\u003csub\u003e6\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e}\u003csup\u003e3+\u003c/sup\u003e, and octameric {[Cu\u003csub\u003e5\u003c/sub\u003eL\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csub\u003e8\u003c/sub\u003e\u0026middot;(PF\u003csub\u003e6\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e}\u003csup\u003e4+\u003c/sup\u003e, respectively. The \u003cem\u003em\u003c/em\u003e/\u003cem\u003ez\u003c/em\u003e values along with isotopic distribution patterns of each charge state closely match the simulated ones (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e), verifying the assignment. These H-bonded oligomers showcase the increasing cluster aggregations concomitant with the associated increase in anions PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e present which bring discrete clusters together into the oligomers. The optimized H-bonded oligomeric structures (Supplementary Fig.\u0026nbsp;6) are quite similar to those observed in the crystallographic data. These H-bonded species are considered as geometric fragments of the icosahedral units, which is primarily important to understand the mechanism of formation of the icosahedral capsule from this reaction system. Especially, detection of the most dominant peak of the trimeric {[Cu\u003csub\u003e5\u003c/sub\u003eL\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csub\u003e3\u003c/sub\u003e\u0026middot;PF\u003csub\u003e6\u003c/sub\u003e}\u003csup\u003e2+\u003c/sup\u003e, is significant, representing the basic trigonal unit of the icosahedron. CSI-MS results indicate that charge-assisted CH\u0026middot;\u0026middot;\u0026middot;F contacts play a pivotal role in the assembly of clusters with anions into identifiable H-bonded oligomers in solution, prior to crystallization.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFascinatingly, each pseudoicosahedral capsule―considered to be a supramolecular secondary building unit―connects with six other icosahedral capsules through sharing bases of isosceles triangles of the pseudoicosahedron, thereby yielding an extended three-periodic zeolitic-like HOFs (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eA), which is the missing link between coinage-metal clusters and HOFs. Of note, topologically, regarding the discrete cluster as a 10-connected node, the whole architecture of the CSF is a unimodal 10-connected framework with the Schl\u0026auml;fli symbol (3\u003csup\u003e16\u003c/sup\u003e.4\u003csup\u003e24\u003c/sup\u003e.5\u003csup\u003e5\u003c/sup\u003e). When viewed in projection down the \u003cem\u003ea\u003c/em\u003e axis, the intricate 3D CSF are seen to contain two types of 1D infinite channels (α and β), as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eB. The α-type channel has cross section of 3.7 \u0026Aring;\u003cem\u003e\u0026times;\u003c/em\u003e7.2 \u0026Aring; to which the phosphine moieties of clusters are exposed, and guest CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solvents were inside the channel. The β-type channel is formed with phenylimidazole arms of clusters and its channel cross section is 7.0 \u0026Aring;\u0026times;7.0 \u0026Aring;. Surprisingly, in the tunnel β, the clusters are arranged to form 1D spirals, with four clusters adopting different rotations per spiral of unit cell length. The spirals in turn are intertwined to give the two strands of an infinite double helix with the same right handedness (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eC). The helical features of the double helix are defined by a pitch length of 5.2 nm and width of 3.6 nm. The entwined strands are stabilized by charge assisted CH\u0026middot;\u0026middot;\u0026middot;F H-bonding interactions between the cationic clusters and anions. The tunnels alongside these double helices are filled with disordered CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e. The existence of guest molecules CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e was also supported by \u003csup\u003e1\u003c/sup\u003eH NMR (Supplementary Fig.\u0026nbsp;2). It is significant to observe that identical supramolecular double helices are produced along \u003cem\u003ea\u003c/em\u003e, \u003cem\u003eb\u003c/em\u003e and \u003cem\u003ec\u003c/em\u003e-axes, respectively, therefore producing unusual mutually perpendicular double helices in three dimensions (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eD). It is worth of noting that it is only recently that 1D double-helical self-assembly has been observed in the realm of coinage metallic clusters aggregates\u003csup\u003e13\u0026ndash;15\u003c/sup\u003e, but no example extending into 3D crystallographic axes have appeared until now. Hence, the superstructure of \u003cb\u003e1\u003c/b\u003e contains another remarkable structural feature of double-stranded helicates which extend in three perpendicular directions, forming 3D orthogonal double-helical patterns, which is advocative of the assembly of double-stranded DNA into various nanostructures in different dimensions\u003csup\u003e36\u0026ndash;38\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eDespite the lack of strong metal-coordination bonds, it is the CSF, achieved by charge-assisted hydrogen bonds, that might exhibit improved stability because of the additional electrostatic attraction between the components\u003csup\u003e39,40\u003c/sup\u003e. To confirm the idea, we accessed the chemical durability of crystals of \u003cb\u003e1\u003c/b\u003e in aqueous solutions with a broad pH range (pH 1\u0026ndash;14). After solid \u003cb\u003e1\u003c/b\u003e was soaked in solutions above-mentioned for three days, there is no obvious difference in morphology and color (Supplementary Fig.\u0026nbsp;7). Crystals of \u003cb\u003e1\u003c/b\u003e still retained their single crystallinity, enabling the SCXRD and their unit-cell parameters are almost identical to that of as-synthesized \u003cb\u003e1\u003c/b\u003e. Moreover, the powder XRD (PXRD) patterns of the sample after prolonged treatment in acidic and basic conditions agree well with the simulated, suggesting that the integrity of the framework is preserved toward both acids and bases (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eA).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThermogravimetric analysis (TGA) profile (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eB) of freshly prepared crystals \u003cb\u003e1\u003c/b\u003e showed the first continuous weight loss stepping from room temperature to ~\u0026thinsp;170 \u0026ordm;C corresponds to the loss of CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e molecules. The superstructure of \u003cb\u003e1\u003c/b\u003e began to decompose at temperature higher than ~\u0026thinsp;215 \u0026ordm;C. To thoroughly understand the thermal stability of the supramolecular framework of \u003cb\u003e1\u003c/b\u003e, we measured variable-temperature PXRD, which revealed that no phase transition or architecture collapse at elevated temperature range 30\u0026ndash;200 \u0026ordm;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eC). The PXRD results reflect an uncharacteristic robustness of the cluster-based H-bonded assembly even after removal of the solvates from channels, where many other noncovalent coinage-metal cluster-based frameworks would fail.\u003c/p\u003e \u003cp\u003eBy slowly heating crystals of \u003cb\u003e1\u003c/b\u003e to 170 \u0026ordm;C under inert atmospheres or in vacuo, \u003cb\u003e1\u003c/b\u003e could be fully desolvated to obtain CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e-free crystals \u003cb\u003e1-d\u003c/b\u003e. The complete removal of guest CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e was also confirmed by \u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy (Supplementary Fig.\u0026nbsp;2), where the chemical shift at 5.25 ppm corresponding to CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e disappears completely after activation. The desolvated crystals \u003cb\u003e1-d\u003c/b\u003e exhibited high thermal stability with negligible weight loss occurred until 215 \u0026ordm;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eB). No significant loss of crystallinity was observed when the CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e molecules were removed gently. The resultant crystals \u003cb\u003e1-d\u003c/b\u003e was successfully examined by X-ray crystallographic analysis, explicitly confirming the single-crystal-to-single-crystal transformation. \u003cb\u003e1-d\u003c/b\u003e retained the same \u003cem\u003eP\u003c/em\u003e\u0026mdash;43n space group as \u003cb\u003e1\u003c/b\u003e, with a shortening of lattice parameters from 26.1645 \u0026Aring; for (\u003cb\u003e1\u003c/b\u003e) to 25.8013 \u0026Aring; (\u003cb\u003e1-d\u003c/b\u003e). The mechanical contraction of the network, with ~\u0026thinsp;2% reduction of the initial unit cell volume, occurs without damaging the crystal upon the removal of CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e. The atomic resolution of SCXRD allows us to discern subtle variations in the CSF before and after heating. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eB, the portal of open channel α\u0026prime; in \u003cb\u003e1-d\u003c/b\u003e kept almost unchanged as observed in the original channel α in \u003cb\u003e1\u003c/b\u003e. Closer examination of channel β\u0026prime; along the \u003cem\u003ea\u003c/em\u003e-direction (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eC), however, revealed structural subtleties, wherein the chelating arrangement of the imidazole plane restricts its rotation, but a clear rotation of the phenyl group attached to the imidazole moiety partially blocks the portal of the open channel β\u0026prime;, resulting in the shrinkage of the resulted window size (4\u0026Aring;\u0026times;4\u0026Aring;). CO\u003csub\u003e2\u003c/sub\u003e adsorption-desorption measurement for \u003cb\u003e1\u003c/b\u003e-\u003cb\u003ed\u003c/b\u003e at 273 K showed a fully reversible type-I Langmuir profile (Supplementary Fig.\u0026nbsp;8), verifying the supramolecular architectural stability and permanent microporous characteristic of \u003cb\u003e1\u003c/b\u003e-\u003cb\u003ed\u003c/b\u003e. It is worth noting that the framework of \u003cb\u003e1\u003c/b\u003e-\u003cb\u003ed\u003c/b\u003e can revert back to its original architecture of \u003cb\u003e1\u003c/b\u003e when recrystallized from CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, featuring structural dynamism of the CSF.\u003c/p\u003e \u003cp\u003eIn general, the cluster-cluster interactions can be tailored via modification of the ligand shell. For \u003cb\u003e1\u003c/b\u003e, due to the inductive effect associated with fluorine atom at the \u003cem\u003epara\u003c/em\u003e-position of benzene, the positively polarized surfaces of the fluorinated aromatics are prone to interact with electron-rich anions. We reasoned that substitution of the \u003cem\u003epara\u003c/em\u003e-F atom with H may be expected to disrupt CH\u0026middot;\u0026middot;\u0026middot;F hydrogen bonds, further markedly affecting the structure of the resulting CSFs. To verify this, we tried to synthesize another analog [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]PF\u003csub\u003e6\u003c/sub\u003e (\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e), by replacing P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e with triphenylphosphine (PPh\u003csub\u003e3\u003c/sub\u003e). X-ray diffraction analysis at 173 K for single crystal of \u003cb\u003e2\u003c/b\u003e established that it occurs in the centrosymmetric tetrahedral space group \u003cem\u003eP\u003c/em\u003e4/\u003cem\u003encc\u003c/em\u003e (No. 130, Supplementary Table S2) with the composition of [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]PF\u003csub\u003e6\u003c/sub\u003e\u0026middot;CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, proved by ESI-MS (Supplementary Fig.\u0026nbsp;9). As anticipated, the cationic cluster [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e is isostructural with [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e. In comparison with \u003cb\u003e1\u003c/b\u003e, however, SCXRD revealed that \u003cb\u003e2\u003c/b\u003e exhibits distinctly different assembly behavior, whereby [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e clusters spontaneously organize into another 3D CSF. The topology of \u003cb\u003e2\u003c/b\u003e can be described as a compressed pcu (primitive cubic) net with nodes as [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e clusters. The basic repeating unit of the 3D CSF contains a double cubane-like cage fused by two same compressed cubic supramolecular cages (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eA), of which each is formed by eight clusters through weak tecton-tecton contacts (i.e., CH\u0026middot;\u0026middot;\u0026middot;π and H\u0026middot;\u0026middot;\u0026middot;H interactions) (Supplementary Fig.\u0026nbsp;10). Interestingly, self-assembled hexafluorophosphate-dichloromethane anionic clusters of [PF\u003csub\u003e6\u003c/sub\u003e\u0026bull;(CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e\u0026minus;\u003c/sup\u003e are docked in the confined cavities of the double cubane-like cage, respectively. Structural characterization reveals that PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e anion in the [PF\u003csub\u003e6\u003c/sub\u003e\u0026bull;(CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e\u0026minus;\u003c/sup\u003e only uses one fluoride atom as quadruple H-bond acceptors to bond with four CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e molecules as single H-bond donor, thereby resulting in four weak nonconventional C-H\u0026middot;\u0026middot;\u0026middot;F hydrogen bonds (\u003cem\u003ed\u003c/em\u003e\u003csub\u003eH\u0026middot;\u0026middot;\u0026middot;F\u003c/sub\u003e = 2.58 \u0026Aring; and \u003cem\u003eθ\u003c/em\u003e\u003csub\u003eC\u0026minus;H\u0026middot;\u0026middot;\u0026middot;F\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;144\u0026deg;). Strikingly, [PF\u003csub\u003e6\u003c/sub\u003e\u0026bull;(CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e\u0026minus;\u003c/sup\u003e has a \u003cem\u003eC\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e symmetry with a 4-fold axis passing through F-P-F of PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e, thus producing two equivalent enantiomers, \u003cem\u003eR\u003c/em\u003e-[PF\u003csub\u003e6\u003c/sub\u003e\u0026bull;(CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e\u0026minus;\u003c/sup\u003e and \u003cem\u003eS\u003c/em\u003e-[PF\u003csub\u003e6\u003c/sub\u003e\u0026bull;(CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e\u0026minus;\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eB). Notably, this is the first structural evidence on chiral PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e-CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e solvated anionic clusters imprisoned in the cage.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe calculated independent gradient model based on Hirshfeld partition (IGMH) analysis on the supramolecular species [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e\u0026bull;PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e indicates the apparent strong CH\u0026middot;\u0026middot;\u0026middot;F interactions in the green section occur between C-H groups of the fluorobenzene rings and F atoms from PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e anion (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eC), which is crucial for the enhanced stability of the rigid supramolecular framework in \u003cb\u003e1\u003c/b\u003e. In contrast, \u003cb\u003e2\u003c/b\u003e does not form the target [Cu\u003csub\u003e5\u003c/sub\u003e\u003cem\u003eL\u003c/em\u003e\u003csub\u003e4\u003c/sub\u003e(PPh\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e\u0026bull;PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e due to negligible weak CH\u0026middot;\u0026middot;\u0026middot;F interactions between PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e and phenyl ring (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eC). On the contrary, the PF\u003csub\u003e6\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e in \u003cb\u003e2\u003c/b\u003e has a high tendency to be solvated by CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e molecules, leading to the formation of solvated anions as discussed above. With the above considerations in mind, we surmised that the absence of strong charge-assisted CH\u0026middot;\u0026middot;\u0026middot;F H-bonding interactions in \u003cb\u003e2\u003c/b\u003e will make the CSF more labile. As anticipated, the crystals \u003cb\u003e2\u003c/b\u003e are extremely fragile, quickly cracked and lost their crystallinity after being taken out of the mother liquor.\u003c/p\u003e \u003cp\u003eSolid-state UV/Vis diffuse-reflectance spectroscopy of the crystalline sample of \u003cb\u003e1\u003c/b\u003e displayed that it is transparent in the visible region of 400\u0026ndash;800 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eD). We investigated the steady-state photoluminescence (PL) spectrum of \u003cb\u003e1\u003c/b\u003e at room temperature, which presented a weak green emission band at around 547 nm upon excitation at 365 nm, with a large Stokes shift (~\u0026thinsp;182 nm). Additionally, the temperature-dependent PL emission was also measured from 300 to 80 K (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eD). The PL spectrum blue-shifted with decreasing temperature from 547 nm at 300 K to 507 nm at 80 K. The corresponding PL intensity enhanced nearly 11-fold. The increased PL intensity upon cooling is a typical phosphorescence characteristic owing to the effective reduction of nonradiative decay at low temperature, whereas the 40-nm hypsochromic-shifted emission may be caused by the restriction of the rotation of the phenyl group attached to the imidazole moiety at low temperature. The emission decay curve monitored at 547 nm gave relatively long lifetimes of 13\u0026ndash;16 ms at 80\u0026ndash;170 K (Supplementary Table S3), which is even visible to the naked eye (inset of Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eD). Both long emission lifetime (millisecond) and large Stokes shift in \u003cb\u003e1\u003c/b\u003e suggest the phosphorescence nature of the green luminescence, primarily originating from a process involved ligand to metal charge transfer (LMCT) or ligand-to-metal-metal charge transfer (LMMCT)\u003csup\u003e41\u0026ndash;43\u003c/sup\u003e.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn conclusion, the results presented here demonstrate for the first time the icosahedral H-bonded nanocapsules assembled from individual clusters. These capsules propagate through edge-sharing into a novel 3D zeolitic-like CSF, offering distinct advantages of being both excellently chemically and thermally stabile. This intrinsic stability can be ascribed to the multiple remarkable charge-assisted CH\u0026middot;\u0026middot;\u0026middot;F hydrogen bonds. This wholly cluster-based H-bonding framework expands the scope of complicated cluster-based supramolecular architectures, and bridges the gap between clusters and HOFs. We expect that this finding can inspire future exploration of the uncovering completely new zeolitic-like CSFs, which may in turn find applications in, for example, gas storage, separation processes, and catalysis.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e \u003cb\u003eSynthesis of 1.\u003c/b\u003e In total, 3 ml CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e/CH\u003csub\u003e3\u003c/sub\u003eOH (v:v\u0026thinsp;=\u0026thinsp;2:1) mixture of copper(II) trifluoroacetate hydrate (43 mg) and tetrabutylammonium hexafluorophosphate (10 mg) were stirred for 10 min. Then P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e (63 mg) and 2-mercapto-1-phenylimidazole (35 mg) were added. With stirring for 15 min, 20 mg NaBH\u003csub\u003e4\u003c/sub\u003e in 1 ml H\u003csub\u003e2\u003c/sub\u003eO, was then added dropwise, which produced a bright red solution. The mixture was stirred for 6h and being aged at 4\u0026deg;C for 12 h. Next, the aqueous phase was removed and the obtained organic phase was washed with H\u003csub\u003e2\u003c/sub\u003eO several times. The resulted solution was centrifuged for 3 min at 10000 r min\u003csup\u003e-1\u003c/sup\u003e and the red-brown solution was filtered. The solution was subjected to diffusion of hexane at room temperature. Colorless crystals were obtained after three days (20% yield, based on Cu).\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of 2. 2\u003c/b\u003e was synthesized by a similar procedure with \u003cb\u003e1\u003c/b\u003e, except the PPh\u003csub\u003e3\u003c/sub\u003e instead of P(C\u003csub\u003e6\u003c/sub\u003eH\u003csub\u003e4\u003c/sub\u003eF)\u003csub\u003e3\u003c/sub\u003e. Colorless crystals were obtained after four days (15% yield, based on Cu).\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eAdditional information\u003c/h2\u003e \u003cp\u003eSupplementary information is linked to the online version of this paper at \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttp://www.nature.com/\u003c/span\u003e\u003cspan address=\"http://www.nature.com/\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e.\u003c/p\u003e \u003c/p\u003e\u003cp\u003e \u003ch2\u003eCompeting interests\u003c/h2\u003e \u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor contributions\u003c/h2\u003e \u003cp\u003eG.G.L. and D.S. conceived and designed the experiments; Z.H.Z., B.L.H. and H.F.S. conducted synthesis and characterization; Z.H.Z., B.L.H., Q.L.G. and W.X.W. researched and analyzed data; J.Q.Z., Y.N.G., J.L.L. and P.C. contributed to scientific discussion; Z.H.Z., B.L.H., G.G.L. and D.S. wrote, reviewed and edited the paper. All authors discussed the results and commented on the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e \u003cp\u003eThis work was financially supported by the National Natural Science Foundation of China (Grant Nos. 91961105, 21641011, 21822107, 21801212), the Natural Science Foundation of Fujian Province (Nos. 2022J01298), the Taishan Scholar Project of Shandong Province of China (Nos. tsqn201812003 and ts20190908), the Natural Science Foundation of Shandong Province (No. ZR2019ZD45, JQ201803 and ZR2017MB061).\u003c/p\u003e\u003ch2\u003eData availability.\u003c/h2\u003e \u003cp\u003eThe X-ray crystallographic coordinates for structures reported in this article have been deposited at the Cambridge Crystal-lographic Data Centre, under deposition number CCDC: 2366513 for \u003cb\u003e1\u003c/b\u003e, 2366514 for \u003cb\u003e1-d\u003c/b\u003e, 2366515 for \u003cb\u003e2\u003c/b\u003e. The data can be obtained free of charge from the Cambridge Crystallographic Data Centre via \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e\u003ca href=\"http://www.ccdc.cam.ac.uk/data_request/cif\" target=\"_blank\"\u003ewww.ccdc.cam.ac.uk/data_request/cif\u003c/a\u003e\u003c/span\u003e\u003cspan address=\"http://www.ccdc.cam.ac.uk/data_request/cif\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eSingharoy A et al (2013) Epitope fluctuations in the human papillomavirus are under dynamic allosteric control: a computational evaluation of a new vaccine design strategy. J Am Chem Soc 135:18458\u0026ndash;18468\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXu N, Gan H-M, Qin C, Wang X-L, Su Z-M (2019) From octahedral to icosahedral metal-organic polyhedra assembled from two types of polyoxovanadate clusters. 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Chem Soc Rev 48:2422\u0026ndash;2457\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":true,"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-4761254/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4761254/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"Hydrogen-bonded assembly of multiple components into well-defined icosahedral capsules akin to virus capsids, has been elusive. In parallel, constructing robust zeolitic-like cluster-based supramolecular frameworks (CSFs) without any coordination bond linkages is challenging. Here, we report the first cluster-based pseudoicosahedral H-bonded capsule Cu60, which is buckled by the self-organization of judiciously designed constituent clusters and anions. The formation of the icosahedron in the solid state takes advantage of 48 charge-assisted CH···F hydrogen bonds between cationic clusters and anions (PF6-), and is highly sensitive to the surface ligands on the clusters with minor structural modification inhibiting its formation. Most excitingly, an extended three-periodic robust zeolitic-like CSF, is inaugurally constructed by edge-sharing the resultant icosahedrons. The perpendicular channels of the CSF feature unusual 3D orthogonal double-helical patterns. The CSF not only keeps its single-crystal character in the desolvated phase, but also exhibits excellent chemical and thermal stabilities as well as long-lived phosphorescence emission.","manuscriptTitle":"Buckling Cluster-based H-Bonded Icosahedral Capsules and Their Propagation to a Robust Zeolite-like Supramolecular Framework","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-08-06 01:35:30","doi":"10.21203/rs.3.rs-4761254/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":"2ac2acf8-4055-422b-9846-ea7579f127c6","owner":[],"postedDate":"August 6th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":35522358,"name":"Physical sciences/Chemistry/Supramolecular chemistry"},{"id":35522359,"name":"Physical sciences/Chemistry/Coordination chemistry"}],"tags":[],"updatedAt":"2024-10-31T07:05:30+00:00","versionOfRecord":{"articleIdentity":"rs-4761254","link":"https://doi.org/10.1038/s41467-024-53640-4","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2024-10-30 04:00:00","publishedOnDateReadable":"October 30th, 2024"},"versionCreatedAt":"2024-08-06 01:35:30","video":"","vorDoi":"10.1038/s41467-024-53640-4","vorDoiUrl":"https://doi.org/10.1038/s41467-024-53640-4","workflowStages":[]},"version":"v1","identity":"rs-4761254","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4761254","identity":"rs-4761254","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}