Buckling cluster-based h-bonded icosahedral capsules and their propagation to a robust zeolite-like supramolecular framework

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 covalent bonding linkages remains challenging. Herein, we report a cluster-based pseudoicosahedral H-bonded capsule

Cu60, which is buckled by the self-organization of judiciously designed constituent copper clusters and anions. The spontaneous 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 protective ligands on the clusters with minor

structural modification inhibiting its formation. Most excitingly, an extended three-periodic robust zeolitic-like CSF, is constructed by edge-sharing the resultant icosahedrons. The

perpendicular channels of the CSF feature unusual 3D orthogonal double-helical patterns. The CSF material 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. SIMILAR CONTENT BEING VIEWED BY OTHERS A THREE-SHELL SUPRAMOLECULAR COMPLEX ENABLES THE

SYMMETRY-MISMATCHED CHEMO- AND REGIOSELECTIVE BIS-FUNCTIONALIZATION OF C60 Article 15 April 2021 SUPRAMOLECULAR POLYNUCLEAR CLUSTERS SUSTAINED CUBIC HYDROGEN BONDED FRAMEWORKS WITH

OCTAHEDRAL CAGES FOR REVERSIBLE PHOTOCHROMISM Article Open access 30 March 2024 PHASE ENGINEERING OF POLYOXOMETALATE ASSEMBLED SUPERSTRUCTURES Article 25 June 2024 INTRODUCTION Nature is

capable of spontaneous association of multiple protein subunits into giant functional superstructures via precise biological self-organization protocols. One accessible and fascinating

natural example is a virus capsid, which is the outer shell of a virus, 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 requirements1. Inspired by this

elegant biology, researchers have recently pursued self-organization through supramolecular interactions, such as metal-coordination bonds, to spontaneously fabricate multiple smaller

subunits into larger artificial nanoconstruct, to mimic viral geometries2,3,4. In this regard, a few cases of icosahedral coordinative capsules have been successfully achieved5,6,7,8,9. 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 strong coordination covalent 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 noncovalent interactions including hydrogen bonds. Supramolecular ensembles are latterly possible with atom-precise

coinage-metal (Cu/Ag/Au) clusters as attractive building blocks. These ultrasmall coinage-metal clusters represent a new category of crystalline materials, which typically consist of a metal

core passivated by a ligand shell. That the library of protective ligands is extensive and affords diverse noncovalent contacts, which directs cluster-cluster assembly to create various

well-defined superstructures10,11,12, including helical aggregates13,14,15,16 and hierarchical assemblies17,18,19,20. Nevertheless, without strong coordinate bonding linkages21,22,23,24,

assembled cluster-based supramolecular systems are relatively fragile and easily collapsed architectures to polycrystallinity, particularly at high temperatures or after the removal of guest

solvents, which has hampered the more extensive study of their potential applications. Additionally, programmed assembly of cluster tectons into sophisticated 3D superstructures and/or

periodic zeolitic-like crystalline supramolecular networks, topologically similar to metal-organic frameworks (MOFs)25,26,27,28,29,30 but conferring a significant advantage of

solution-processability, poses a formidable challenge. The main reason comes from the complexity of intercluster interactions, and/or the lack of suitable cluster modules and

structure-directing forces. Based on the above considerations, in this work, we report the discovery of cluster-based H-bonded pseudo icosahedral capsules Cu60 spontaneously formed through

the assembly of cationic copper clusters and anions (PF6−), by means of 48 charge-assisted CH···F hydrogen bonds. The key geometric fragments of the icosahedron could be detected by

cold-spray ionization mass spectrometry (CSI-MS), which provides insight into the underlying rules of multicomponent H-bonded assembly. Moreover, each intrinsic hollow icosahedral capsule is

connected to six adjacent equivalent ones by edge-sharing to generate a robust three-periodic zeolitic-like supramolecular architecture with extrinsic helical channels, conferring thermal

durability, and resistance to acids and bases. The resulting assembled 3D superstructure, referred to as cluster-based supramolecular frameworks (CSFs), gives a case of controlling

assemblies of stable zeolitic-like cluster-based supramolecular solids without utilizing strong covalent and coordinate bonding linkage, and is an emerging link between coinage-metal

clusters and hydrogen-bonded organic frameworks (HOFs). RESULTS SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF CLUSTER-BASED TECTONS Actively seeking accessible construction strategies to

create 3D stable crystalline CSFs, our attention was initially captivated by robust HOFs materials, such as well-known HOF-1 that relies on the H-bonded assembly of purely organic tectons

with tetrahedral geometry to form 3D crystalline networks31,32. Taking inspiration from structural 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 tetrahedral

copper cluster [Cu5L4((_p_-F-Ph)3P)4]PF6 (1) (where 2-mercapto-1-phenylimidazole = HL, and (_p_-F-Ph)3P = tris(4-fluorophenyl) phosphine) through reducing the copper salts with NaBH4 in the

presence of HL and (_p_-F-Ph)3P under ambient conditions. The cluster structure of 1 was firstly elucidated by NMR spectroscopy, of which 1H 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 were further confirmed by electrospray ionization mass

spectrometry (ESI-MS) in positive mode (Supplementary Fig. 3 and Supplementary Table 1). The parent cluster ion was found at the most dominant peak, _m_/_z_ 2283.0142, which could be

identified with isotopic envelopes corresponding to [Cu5L4((_p_-F-Ph)3P)4]+ (calc. _m_/_z_ = 2283.0307). Density functional theory (DFT) optimized structure of [Cu5L4((_p_-F-Ph)3P)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 the experimental UV/Vis absorption spectrum of 1 measured in dichloromethane (CH2Cl2), which showed two major UV absorption bands at 358 and 368 nm and a tail up to about 400 nm

(Supplementary Fig. 5), indicating the cluster retains intact in solution. Colorless crystals of 1 suitable for X-ray crystallography were obtained by slow vapor diffusion of _n_-hexane into

a concentrated CH2Cl2 solution of the corresponding cluster (PF6− salt) at ambient temperature. Microscopic image of single crystals, exhibit rhombic dodecahedra shape with twelve

well-defined diamond facets (Fig. 1a). Single-crystal X-ray diffraction (SCXRD) analysis revealed that 1 crystallizes in the higher-symmetry cubic crystal system with the non-centrosymmetric

space group \(P {\bar{4}}\) 3n (No. 218, Supplementary Table 2). Its overall composition contains a cationic cluster [Cu5L4((_p_-F-Ph)3P)4]+, as well as one PF6− counterion and interstitial

CH2Cl2 molecules. As portrayed in Fig. 1b, the structural anatomy of [Cu5L4((_p_-F-Ph)3P)4]+ can be viewed as a Cu5 kernel wrapped by four peripheral (_p_-F-Ph)3P and four deprotonated L−

ligands. The metal core adopts a centered tetrahedral geometry. The Cu-Cu bond length in the metal skeleton from the central Cu atom to the vertexes of the Cu4 tetrahedron is equal (2.655(1)

Å), suggestive of the presence of significant intramolecular cuprophilic interactions. It is worthy of note that such a centered tetrahedral Cu5 skeleton is quite unusual, as a Cambridge

Structural Database (CSD) search33 yielded previously reported some discrete Cu5 clusters featuring a planar conformation or a bipyramidal geometry (Fig. 1c)34,35. The center Cu atom is

tetrahedrally bonded to all four L− molecules via four Cu-S bonds, while each terminal Cu atom in the Cu4 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_-F-Ph)3P. Thus, the entire cationic cluster lies in a special position with _S_4 symmetry. CRYSTALLINE CLUSTER-BASED H-BONDED ICOSAHEDRAL

ASSEMBLY Inspection of the rhombic dodecahedral crystal habit in the case of 1 is unexpected among crystalline forms of coinage metallic clusters, which is evocative of an example of

icosahedral viruses crystallized into cubic crystals in a similar dodecahedral shape36. This 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 molecular copper clusters per unit cell self-assemble into an enclosed approximately icosahedral capsule

denoted as Cu60 (Fig. 1d) with an approximate diameter of 3.0 nm. The surface of the pseudo icosahedron contains two types of triangular faces (Fig. 1e): 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. It is worth noting that this is the only possible combinatorial outcome for the pseudo icosahedron buckled from these equilateral triangles and isosceles

triangles, based on the ChatGPT prediction37. The internal hollow icosahedral capsule Cu60 could accommodate a sphere with a diameter of about 25 Å, corresponding to a sphere volume of ~8177

 Å3. Our observation of the supramolecular icosahedral assembly that involves solid-state aggregation of individual clusters is intriguing. It was previously reported that atomically precise

metal nanoclusters functionalized with capsid-targeting ligands which were used to label specific components of the surface of enteroviruses created icosahedral arrangement of

clusters38,39. But once the absence of capsid-targeting ligands and without linking to the viral surfaces, cluster-based icosahedra are difficult to achieve. More importantly, the atomically

accurate cluster-based icosahedral capsule will provide much more detailed information for further identifying the possible assembled origin of the icosahedron as the largest of the

Platonic solids. Figure 1f shows the electrostatic potential (ESP) mapped onto the electron isodensity surface of [Cu5L4((_p_-F-Ph)3P)4]+. It is calculated that the surface ESP is highly

positive and may be strongly inclined to interact with negatively charged species (i.e., counter anions) to make supramolecular assemblages. As a result, PF6− counterions lie at the center

of equilateral triangles of the icosahedron, wherein half fluoride atoms of each PF6− anion interact with three neighboring [Cu5L4((_p_-F-Ph)3P)4]+ clusters to form a supramolecular trimer

(Fig. 1g). Each copper cluster located at the vertice of icosahedron could be visualized as two parts, a Cu(_p_-F-Ph)3P and a Cu3L4((_p_-F-Ph)3P)3 moiety, which points inside and outside the

surface of icosahedral capsule, respectively. As illustrated in Fig. 1g, a closer inspection of the intermolecular contact patterns reveals each F atom of the PF6− participates in two

H-bonds with two fluorobenzenes from two neighboring Cu(_p_-F-Ph)3P 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 crystals40. In total, the icosahedral capsule is held together by way of 48 CH···F hydrogen bonds. Such

cluster-based icosahedral H-bonded capsule Cu60 is reminiscent of copies of identical protein clusters assembled into icosahedral viral capsids. As mentioned at the outset, some discrete

supramolecular coordinative icosahedral entities have been identified, such as molybdenum oxide cluster Mo1325 and metal-organic capsule Fe126,7. However, bonding energy for hydrogen bonds

(25–40 kJ mol−1)41,42 is generally much smaller than those of coordinate covalent bonds (90–350 kJ mol−1)42, making well-defined H-bonded icosahedrons more challenging to assembly than their

coordination counterparts. It is especially interesting to note the icosahedral Cu60 shows distinct trigonal types, which are different from those observed in the face-directed coordinative

icosahedra. The trigonal panels of the former which are constructed from anions hydrogen-bonded to cationic clusters produce interesting _C_3-symmetric facial chirality (Fig. 1g), while the

trigonal faces of the latter are generated from planar tritopic linkers coordination-bonded to metal acceptors (Supplementary Fig. 6)6,7. Additionally, from the view of capsule size, the

diameter of the supramolecular H-bonding capsule Cu60 is 3.0 nm, making it comparable to that of the nanosized icosahedral Mo132 (2.9 nm). CSI-MS CHARACTERIZATION 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 CH2Cl2, in which the ion source temperature is 0 °C. 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 {[Cu5L4((_p_-F-Ph)3P)4]3·PF6}2+, pentameric {[Cu5L4((_p_-F-Ph)3P)4]5·(PF6)2}3+, and octameric

{[Cu5L4((_p_-F-Ph)3P)4]8·(PF6)4}4+, respectively. The _m_/_z_ values along with isotopic distribution patterns of each charge state closely match the simulated ones (Fig. 2), verifying the

assignment. These H-bonded oligomers showcase the increasing cluster aggregations concomitant with the associated increase in anions PF6− present which bring discrete copper clusters

together into the oligomers. The optimized H-bonded oligomeric structures (Supplementary Fig. 7) are quite similar to those observed in the crystallographic data. These H-bonded species are

considered as key geometric fragments of the icosahedral units, which is primarily important to understand the mechanism of formation of the icosahedral capsules from this reaction system.

Especially, the detection of the most dominant peak of the trimeric {[Cu5L4((_p_-F-Ph)3P)4]3·PF6}2+, is significant, which represents the basic trigonal unit of the icosahedron. CSI-MS

results indicate that the charge-assisted CH···F contacts play a pivotal role in the assembly of copper clusters coupling with anions into identifiable H-bonded oligomers in solution, prior

to crystallization. 3D ROBUST ZEOLITIC-LIKE CSFS Fascinatingly, each pseudo icosahedral capsule―considered to be a supramolecular secondary building unit―connects with six other icosahedral

ones through sharing bases of isosceles triangles of the pseudo icosahedron, thereby yielding an extended three-periodic zeolitic-like CSF (Fig. 3a), which sets it apart from HOFs and MOFs.

Of note, topologically, if each discrete cluster is regarded as a 10-connected node, the whole architecture of the CSF is an unimodal 10-connected framework with the Schläfli symbol

(315.423.55). When viewed in projection down the _a_ axis, the intricate 3D CSF is seen to contain two types of 1D infinite channels (α and β). As illustrated in Fig. 3b, the α-type channel

has a cross-section of 3.7 Å _×_ 7.2 Å to which the phosphine moieties of clusters are exposed, and guest CH2Cl2 solvents are 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 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. 3c). 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 CH2Cl2. The existence of guest molecules CH2Cl2 was also supported by 1H 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. 3d). 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 aggregates13,14,15,16. Hence, the superstructure of 1 contains another 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 dimensions43,44,45. 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 components46,47. 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 the

solutions above-mentioned for three days, there was no obvious difference in morphology and color (Supplementary Fig. 8). 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. 4a). Thermogravimetric analysis (TGA) profile

(Fig. 4b) of freshly prepared crystals 1 showed the first continuous weight loss stepping from room temperature to ~170 °C corresponds to the loss of CH2Cl2 molecules. The superstructure of

1 began to decompose at a temperature higher than ~215 °C. To thoroughly understand the thermal robustness of the CSF of 1, we measured variable-temperature PXRD, which revealed that no

phase transition or architecture collapse at elevated temperature range 30–200 °C (Fig. 4c). The PXRD results reflect an uncharacteristic robustness of the cluster-based H-bonded assembly

even after removal of the occluded solvent molecules from channels, where many other noncovalent coinage-metal cluster-based frameworks would fail. By slowly heating crystals of 1 to 170 °C

under inert atmospheres or in vacuo, to our delight, 1 could be fully desolvated to obtain CH2Cl2-free crystals 1-D. The complete removal of guest CH2Cl2 was also confirmed by 1H NMR

spectroscopy (Supplementary Fig. 2), where the chemical shift at 5.25 ppm corresponding to CH2Cl2 disappears completely after activation. The desolvated crystals 1-D exhibited high thermal

stability with negligible weight loss occurred until ~215 °C (Fig. 4b). No significant loss of crystallinity was observed when the CH2Cl2 molecules were removed gently. The resultant

crystals 1-D were successfully examined by X-ray crystallographic analysis, explicitly confirming the single-crystal-to-single-crystal transformation. 1-D retained the same \(P {\bar{4}}\)

3n space group (Supplementary Table 2) as 1, with shortened 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 full removal of occluded CH2Cl2. The atomic resolution of SCXRD allows us to discern subtle variations in the CSF

before and after heating. As displayed in Fig. 3b, 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. 3c), 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 (4 Å × 4 Å). CO2

adsorption-desorption measurement for 1-D at 273 K showed a fully reversible type-I Langmuir profile (Supplementary Fig. 9), verifying the supramolecular architectural stability and

permanent microporous characteristic of 1-D. Notably, the framework of 1-D can revert to its original architecture of 1 when simply recrystallized from CH2Cl2, featuring the structural

dynamism and regeneration ability of the CSF. EFFECT OF LIGAND ON THE CSF In general, the cluster-cluster interactions can be tailored via modification of the protective shield of ligands.

For 1, due to the inductive effect associated with the 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 atom may be expected to disrupt CH···F hydrogen bonds, further markedly affecting the structure and

stability of the resulting CSFs. To verify this, we tried to synthesize another analog [Cu5L4(PPh3)4]PF6 (2), by replacing P(C6H4F)3 with triphenylphosphine (PPh3), under identical synthesis

conditions. X-ray diffraction analysis at 173 K for a single crystal of 2 established that it occurs in the centrosymmetric tetragonal space group _P_4/_ncc_ (No. 130, Supplementary Table 

3) with the composition of [Cu5L4(PPh3)4]PF6·CH2Cl2, proved by ESI-MS (Supplementary Fig. 10 and Supplementary Table 4). As anticipated, the cationic cluster [Cu5L4(PPh3)4]+ is isostructural

with [Cu5L4((_p_-F-Ph)3P)4]+. In comparison with 1, however, SCXRD revealed that 2 exhibits distinctly different cluster-based assembly behavior, whereby [Cu5L4(PPh3)4]+ clusters

spontaneously organize into another 3D CSF. The topology of 2 can be described as a compressed pcu (primitive cubic) net with nodes defined as [Cu5L4(PPh3)4]+ clusters. The basic repeating

unit of the 3D CSF contains a double cubane-like cage fused by two same compressed cubic supramolecular cages (Supplementary Fig. 11), of which each is formed by eight clusters through weak

tecton-tecton contacts (i.e., weak CH···π and H···H interactions) (Supplementary Fig. 12). Interestingly, self-assembled hexafluorophosphate-dichloromethane anionic clusters of

[PF6·(CH2Cl2)4]− are docked in the confined cavities of the double cubane-like cage, respectively. Structural characterization reveals that PF6− anion in the [PF6·(CH2Cl2)4]− only uses one

fluoride atom as quadruple H-bond acceptors to bond with four CH2Cl2 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, [PF6·(CH2Cl2)4]− has a _C_4 symmetry with a 4-fold axis passing through F-P-F of PF6−, thus producing two equivalent enantiomers, _R_-[PF6·(CH2Cl2)4]−

and _S_-[PF6·(CH2Cl2)4]− (Supplementary Fig. 13). Notably, this is the structural evidence on chiral PF6−-CH2Cl2 solvated anionic clusters imprisoned in the supramolecular cage. The

calculated independent gradient model based on Hirshfeld partition (IGMH) analysis on the supramolecular species {[Cu5L4((_p_-F-Ph)3P)4]+·PF6−} indicates the apparent strong CH···F

interactions in the green section occur between C–H groups of the fluorobenzene rings and F atoms from PF6− anion (Fig. 5a), which is crucial for the enhanced stability of the rigid

supramolecular framework in 148,49,50. In contrast, 2 does not form the stable target {[Cu5L4(PPh3)4]+·PF6−} due to calculated negligible weak CH···F interactions between PF6− and phenyl

rings (Fig. 5a). On the contrary, the PF6− in 2 has a high tendency to be solvated by CH2Cl2 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 its crystallinity after being taken out of the mother liquor. SOLID-STATE OPTICAL AND LUMINESCENCE PROPERTIES 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. 5b). Subsequently, we investigated the steady-state photoluminescence

(PL) spectra of 1 at room temperature, which presented a weak green emission band at around 547 nm upon excitation at 365 nm, with a substantial Stokes shift (~182 nm). Additionally, the

temperature-dependent PL measurements were conducted from 300 to 80 K (Fig. 5b). The PL emission intensity is enhanced as the temperature changes from 300 to 80 K. A significant blue shift

was observed from 547 to 510 nm with the temperature decrement. The increased emission intensity upon cooling is a typical phosphorescence characteristic owing to the effective reduction of

nonradiative pathways 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. Remarkably, the time-resolved PL decay curve gave relatively long lifetimes of 13–16 ms at 80–170 K (Supplementary Table 5), and the green afterglow was visible to

the naked eyes over 0.8 s after switching off the UV lamp (Fig. 5c). Both long emission lifetime (millisecond) and large Stokes shift in 1 suggest the green emission mechanism is

phosphorescence-type, primarily emanating from a process involved ligand-to-metal charge transfer (LMCT) or ligand-to-metal-metal charge transfer (LMMCT)51,52,53. Of note, the

millisecond-long emission with obvious afterglow in crystalline 1 surpasses other thiolate-protected luminescent copper clusters with microsecond lifetimes53,54,55,56, which are difficult to

observe by the naked eyes after removing the light source. DISCUSSION In summary, the results presented here demonstrate that the icosahedral H-bonded nanocapsules can be assembled from

individual clusters featuring with tetrahedral metal cores and anions. These capsules further propagate through edge-sharing into a 3D zeolitic-like CSF, offering the distinct advantages of

being both excellently chemically and thermally stable. This intrinsic stability can be ascribed to the multiple 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 coinage-metal clusters and HOFs. We expect that this finding can inspire

future exploration of the uncovering zeolitic-like CSFs, which may in turn find applications in, for example, gas storage, separation processes, and catalysis. METHODS SYNTHETIC PROCEDURE

FOR 1 3.0 mL CH2Cl2/CH3OH (_v_:_v_ = 2:1) solution containing copper(II) trifluoroacetate hydrate (43.4 mg, 0.15 mmol) and tetrabutylammonium hexafluorophosphate (11.6 mg, 0.03 mmol) was

stirred for 10 min, and then (_p_-F-Ph)3P (63.2 mg, 0.2 mmol) and 2-mercapto-1-phenylimidazole (35.0 mg, 0.2 mmol) were added under vigorous stirring. After stirring for another 15 min, a

freshly prepared solution of NaBH4 (20.0 mg dissolved in 1.0 mL water) was added dropwise to the mixture under vigorous stirring. The reaction continued for 6 h at room temperature and aged

at 4 °C for 12 h. Next, the aqueous phase was removed and the obtained organic phase was washed with water for several times. Finally, the resulted solution was centrifuged for 3 min at

10000 rpm min−1, and the red-brown solution was filtered. Dodecahedral rhombohedral colorless crystals of 1 were obtained via slow diffusion of _n_-hexane into the cluster solution after

three days (20% yield based on Cu). Elemental analysis (%) calcd for C109H78S4P4F12N8Cl2Cu5: C 55.27, H 3.32, N 4.73; Found: C 54.84, H 3.15, N 4.42. High-resolution ESI-MS: _m_/_z_ = 

2283.0307 ([Cu5(C9H8N2S)4(P(C6H4F)3)4]+). SYNTHETIC PROCEDURE FOR 2 2 was synthesized by a similar procedure of 1, except PPh3 (52.6 mg, 0.2 mmol) instead of (_p_-F-Ph)3P. Block colorless

crystals were obtained after four days (14% yield based on Cu). Elemental analysis (%) calcd for C108H88S4P5F6N8Cu5: C 58.62, H 4.01, N 5.06; Found: C 58.93, H 3.95, N 4.75. High-resolution

ESI-MS: _m_/_z_ = 2067.173 ([Cu5(C9H8N2S)4(P(C6H5)3)4]+). DATA AVAILABILITY All data that support the findings of this study are available within the paper and its supplementary information

files, and also available from the corresponding author upon request. Crystallographic data for structures reported in this article have been deposited at the Cambridge Crystallographic Data

Centre (CCDC), under deposition numbers CCDC 2366513 (1), 2366514 (1-D), and 2366515 (2). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All

other data supporting the findings of the study, including experimental procedures and compound characterization, are available within the paper and its Supplementary Information, or from

the corresponding author upon request. Coordinates of the optimized structures are provided in the source data file. Source data are provided with this paper. REFERENCES * Edwardson, T. G.

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implications for optoelectronic applications. _ACS Appl. Nano Mater._ 7, 32–60 (2024). Article  CAS  Google Scholar  Download references ACKNOWLEDGEMENTS This work was financially supported

by the National Natural Science Foundation of China (Nos. 92361301, 22325105, 52261135637, 22171164), the Natural Science Foundation of Fujian Province (No. 2022J01298). We thank Dr.

Shu-Ting Wu (Fuzhou University) and Prof. Da-Qiang Yuan (Fujian Institute of Research on the Structure of Matter) for valuable discussions and assistance in chirality and topology analysis.

The Instrumental Analysis Centre of Huaqiao University for analytical characterization is also acknowledged. AUTHOR INFORMATION Author notes * These authors contributed equally: Zhan-Hua

Zhao, Bao-Liang Han. AUTHORS AND AFFILIATIONS * College of Materials Science and Engineering, Huaqiao University, Xiamen, PR China Zhan-Hua Zhao, Qi-Lin Guo, Jing-Qiu Zhuo, Yong-Nan Guo, 

Jia-Long Liu & Geng-Geng Luo * Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal

Materials, Shandong University, Jinan, PR China Bao-Liang Han, Wen-Xin Wang, Ping Cui & Di Sun * College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, PR China

Hai-Feng Su Authors * Zhan-Hua Zhao View author publications You can also search for this author inPubMed Google Scholar * Bao-Liang Han View author publications You can also search for this

author inPubMed Google Scholar * Hai-Feng Su View author publications You can also search for this author inPubMed Google Scholar * Qi-Lin Guo View author publications You can also search

for this author inPubMed Google Scholar * Wen-Xin Wang View author publications You can also search for this author inPubMed Google Scholar * Jing-Qiu Zhuo View author publications You can

also search for this author inPubMed Google Scholar * Yong-Nan Guo View author publications You can also search for this author inPubMed Google Scholar * Jia-Long Liu View author

publications You can also search for this author inPubMed Google Scholar * Geng-Geng Luo View author publications You can also search for this author inPubMed Google Scholar * Ping Cui View

author publications You can also search for this author inPubMed Google Scholar * Di Sun View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS

G.-G.L. and D.S. conceived and designed the experiments; Z.-H.Z., and B.-L.H. and H.-F.S. conducted synthesis and characterization; Z.-H.Z., B.-L.H., Q.-L.G., W.-X.W., and G.-G.L. researched

and analyzed data; J.-Q.Z., Y.-N.G., J.-L.L., and P.C. contributed to scientific discussion; Z.-H.Z., G.-G.L. and D.S. wrote the manuscript. All authors discussed the results and commented

on the manuscript. CORRESPONDING AUTHORS Correspondence to Geng-Geng Luo or Di Sun. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. Reprint and

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H-bonded icosahedral capsules and their propagation to a robust zeolite-like supramolecular framework. _Nat Commun_ 15, 9401 (2024). https://doi.org/10.1038/s41467-024-53640-4 Download

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