Silvery fullerene in Ag102 nanosaucer

ABSTRACT Despite the discovery of a series of fullerenes and a handful of noncarbon clusters with the typical topology of Ih-C60, the smallest fullerene with a large degree of curvature, C20, and its other-element counterparts are difficult to isolate experimentally. In coinage metal nanoclusters (NCs), the first all-gold fullerene, Au32, was discovered after a long-lasting pursuit, but the isolation of similar silvery fullerene structures is still challenging. Herein, we report a flying saucer-shaped 102-nuclei silver NC (Ag102) with a silvery fullerene kernel of Ag32, which is embraced by a robust cyclic anionic passivation layer of (KPO4)10. This Ag32 kernel can be viewed as a non-centered icosahedron Ag12 encaged into a dodecahedron Ag20, forming the silvery fullerene of Ag12@Ag20. The anionic layer (KPO4)10 is located at the interlayer between the Ag32 kernel and Ag70 shell, passivating the Ag32 silvery fullerene and templating the Ag70 shell. The tBuPhS− and CF3COO− ligands on the silver shell show a regioselective arrangement with the 60 tBuPhS− ligands as expanders covering the upper and lower of the flying saucer and 10 CF3COO− as terminators neatly encircling the edges of the structure. In addition, Ag102 shows excellent photothermal conversion efficiency (η) from the visible to near-infrared region (η = 67.1% ± 0.9% at 450 nm, 60.9% ± 0.9% at 660 nm and 50.2% ± 0.5% at 808 nm), rendering it a promising material for photothermal converters and potential application in remote laser ignition. This work not only captures silver kernels with the topology of the smallest fullerene C20, but also provides a pathway for incorporating alkali metal (M) into coinage metal NCs via M-oxoanions.


INTRODUCTION
The persistent fascination with coinage metal nanoclusters (NCs) arises from their remarkable structural diversity involving the distinctive metal lophi licity and their promising applications in catalysis, luminescence, biomedicine, as well as chemical sensing [1 -9 ].Understanding the precise structure is of utmost importance as it holds the key to advancing our knowledge about the evolution from a discrete metal atom to a solid state [10 -16 ].In 2004, Johansson, Gong, et al. made a noteworthy prediction, suggesting that the most stable structure of the Au 32 cage would be a hollow structure with icosahedral ( I h ) symmetry and a diameter of ∼0.9 nm [17 ,18 ].The synthesis and total structure determination of golden fullerene were carried out by Wang and Schnepf's groups in 2019, employing the direct reduction of the Au precursor by NaBH 4 and X-ray crystallography characterization [19 ,20 ].This marked the emergence of the first all-gold fullerene species.In light of the successful elucidation of the golden fullerene, can the silvery fullerene with a similar topology be achieved?A fullerene-like silver NC of A g 13 @A g 20 was previously reported, but the inner kernel is a centered-icosahedral A g@A g 12 solid rather than a hollow cage and the outer dodecahedral shell is distorted, which deviates from the ideal fullerene topology [21 ].Over the past decades, a popular synthetic strategy for silver NCs was the bottom-up approach involving the chemical reduction of silverligand complexes in solution or the introduction of directing agents to facilitate the aggregation of silver ions [22 ,23 ].Significant progress has been achieved for organic ligand-protected silver NCs such as the largest silver cage, Ag 180 , and the largest silver nanoparticle, Ag 374 [24 ,25 ], both of which were characterized by X-ray crystallography.Despite significant efforts dedicated to synthesizing and elucidating the structure of silver NCs, the total structural determination of silvery fullerene Ag 32 remains pending.
Recently, N , N -dimethylformamide (DMF) has demonstrated efficacy as a mild reductive agent, slowing down the reductive rate of silver ions to atoms, then decelerating the aggregation rate of silver atoms into nanoparticles.This, in turn, enables oxoanions to passivate the highly active silver aggregates.As a matter of fact, nanoscale icosahedral silver nanocrystals can be produced by the reduction of AgNO 3 /PVP in DMF [26 ].If downsizing the icosahedral silver nanocrystal to the molecular level, it yields the dual polyhedron Ag 12 of Ag 20 with minimal fullerene topology, promising the potential to obtain the structure of silvery fullerene A g 12 @A g 20 by using DMF as the reductive agent.Our group has successfully isolated a series of silver NCs that encapsulated different silver kernels, such as [Ag 6 @(CrO 4 ) 8 @Ag 52 ], [Ag 10 @(Mo 7 O 26 ) 2 @A g 70 ], [A g 6 @(MoO 4 ) 7 @A g 56 ] and [A g 13 @A g 76 S 16 ( p -NH 2 -PhAsO 3 ) 4 ], which display the excellent abilities of anionic templates in passivating the inner silver kernel and supporting the outer silver shell [27 -30 ].However, the trapping of silvery fullerene structures has not yet been observed, which may be related to the incompatibility of the silver kernel with the oxoanionic passivation layer.Considering that both coinage and alkali metal (M) atoms have a valence shell s 1 electronic configuration [31 ], it is plausible that the M could be incorporated into the silver NCs to support the overall structure [32 -34 ].However, alkali and coinage metal atoms differ greatly in terms of atomic radius size and standard reduction potential [35 ], presenting substantial challenges for incorporating M into silver NCs.Zheng et al. reported the first case regarding the incorporation of M into an alkynylstabilized coinage-metal NC, a body-centered cubic (bcc) structure of [Au 7 Ag 8 (C ≡C t Bu) 12 ] + and the substitution chemistry of that cluster was well studied by electrospray ionization mass spectrometry (ESI-MS) and density functional theory (DFT) calculations, but the single-crystal structure involving the M incorporation has not been available [31 ].We envision that oxygenphilic M may be incorporated into the silver NCs through M-O bonding to form an M-oxoanions passivation layer to capture the si lvery ful lerene.Based on the above considerations, the isolation of the si lvery ful lerene by M-oxoanions is significant but ful l of chal lenges.
To achieve this objective, with the endeavor to introduce rarely utilized KH 2 PO 4 species in the assembly of silver NCs, we successfully isolated a giant 102nuclei silver NC ( Ag102 ) with an unprecedented silvery fullerene kernel.In a shape resembling a flying saucer, Ag102 has the following features: (i) a robust anionic cyclic passivation layer of (KPO 4 ) 10 trapping a si lvery ful lerene kernel of Ag 32 ; (ii) the first Ag-K bimetallic NC at atomic precision level; (iii) regiospecific distribution of t BuPhS − and CF 3 COO − ligands on the silver shell.

RESULTS
The preparative route of Ag102 involved the direct reduction of a mixture of {(HNEt 3 ) 2 [Ag 10 ( t BuPhS) 12 ]} n , p -tertbutylthiacalix [4]arene (H 4 TC4A), CF 3 COOAg and KH 2 PO 4 in the aprotic solvent DMF.Black rod-like crystals suitable for X-ray diffraction were obtained after DMF-thermal reaction (Scheme 1 ).Detailed synthetic procedures are provided in the Supplementary Information (SI).In the synthetic process, DMF serves a dual role both as a solvent to facilitate the dissolution of the above-mentioned reactants, and as a mild reducing agent to promote the reduction of Ag + , followed by the formation of embryonic silver kernels in a controllable manner.To the best of our knowledge, the si lvery ful lerene of Ag 32 captured in Ag102 is the largest subvalent silver kernel with DMF as the mild reducing agent ( Table S1).Although the H 4 TC4A ligand is not involved in the final structure of Ag102 , the black precipitate was exclusively obtained in the absence of it, indicating its important role in the formation of Ag102 .The possible reason was that H 4 TC4A first reacted with Ag(I) to form the intermediate Ag-TC4A complex, which can slow down the release rate of Ag(I) ions to further diminish the reduction kinetics of DMF, finally forming a medium-sized subvalent silver kernel.

Crystal structure of Ag 102
Single-crystal X-ray diffraction (SCXRD) analysis revealed that Ag102 crystallized in a monoclinic space group I 2/ m with the formula of [A g 12 @A g 20 @(KPO 4 ) 10 @A g 70 ( t BuPhS) 60 (CF 3 COO) 10 (DMF) 2 ].The entire Ag102 looks like a flying saucer and exhibits a pseudo-5-fold symmetry (Fig. 1 ).The equatorial diameter and axial thickness of the silver skeleton are 2.3 and 0.6 nm, respectively.The high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images reveal that the average size of the nanoparticles is ∼2.2 nm ( Fig. S1), in agreement with the equatorial diameter (2.3 nm) of Ag102 determined by SCXRD (Fig. 1 a).There are two Ag 102 molecules in a unit cell, one at the apex and the other at the center ( Fig. S2).In detail, the structure of Ag102 features a three-layered structure with an A g 12 @A g 20 si lvery ful lerene as the subvalent kernel, a (KPO 4 ) 10 anionic layer, and an Ag 70 shell from inner to outer.The Ag 70 shell is protected by the binary organic ligands of t BuPhS − and CF 3 COO − .
For a more elaborate anatomy of the structure, we start with the innermost par t, Ag 12 .As por trayed in Fig. 2 a and b, the Ag 12 is a hollow icosahedron.In contrast to the most observed non-hollow icosahedral Ag 13 kernel, the hollow icosahedral Ag 12 kernel in Ag102 is also an important nano-building block of silver NCs, as observed in Ag 44 (SR) 12 , Ag 50 (dppm) 6 (SR) 30 , etc [36 -38 ].The Ag•••Ag distance in Ag 12 falls in the range of 2.748-2.847Å (average: 2.808 Å).Subsequently, an Ag 20 dodecahedron completely embraces the Ag 12 hollow icosahedral cage forming a silvery fullerene kernel (A g 12 @A g 20 ).In this configuration, the icosahedron and its dual (the dodecahedron) with I h symmetry are thus compatible, and each silver atom of Ag 12 is directed toward the center of the pentagon in the Ag 20 dodecahedron (Fig. 2 c, d).The A g•••A g distances between Ag 12 and Ag 20 are in the range of 2.760-2.986Å (average: 2.847 Å; Fig. S3).The 30 A g•••A g edge leng ths in the A g 20 fall in the range of 3.005-3.481Å, of which 10 longer A g•••A g edges (two in 3.349 Å, four in 3.359 Å and four in 3.481 Å) were elongated by the coordination of t BuPhS − .The size of the Ag 20 is ∼7.1 Å, identical in size to its famous all-carbon fullerene cousin, C 60 , and slightly shorter than the size of [K@Au 12 Sb 20 ] 5 − ( Fig. S4) [39 -41 ].The anionic passivation layer of (KPO 4 ) 10 situated at the waist of A g 12 @A g 20 plays a dual role of passivating the inner A g 12 @A g 20 kernel and supporting the outer Ag 70 shell.There are no other organic ligands except two DMF molecules that penetrated the Ag 20 top and bottom pentagons and anchored on the top and bottom silver atoms of the Ag 12 hollow cage with Ag-O DMF bond distances of 2.334 Å.Each of the remaining 10 pentagon faces of the Ag 20 dodecahedron is coated with a K +  ion, resulting in the formation of a K 10 pentagonal antiprism, which can be derived from the regular icosahedron by cutting off two opposite vertices ( Figs S5, S6).Each PO 4 3 − rides on the K-K edge of the waist of the K 10 pentagonal antiprism and ligates two K atoms via two of the four O atoms to form the (KPO 4 ) 10 cyclic anionic layer (Fig. 2 e, f).One PO 4 3 − can attach six silver atoms, two of the Ag 20 dodecahedron and four of the outer Ag 70 shell, giving the coordination pattern of μ 8 -κ 3 : κ 3 : κ 1 : κ 1 (Ag-O: 2.254-2.504Å and K-O: 2.224-2.352Å) (Fig. 2 g, h).
From the polygon view, the outer conchshaped Ag 70 shell is composed of silver trigons and tetragons, revealing an intriguing interfacial binding profile, with t BuPhS − acting as expanding ligands covered on the Ag 4 tetragons and Ag 3 trigons at the up and down of the conch, and CF 3 COO − as terminating ligands which seamed the periphery, respectively ( Figs S7 , S8).The surface protection patterns can be divided into four hierarchies from the apex to the equator: A g 20 S 10 , A g 30 S 20 , A g 20 S 30 and terminating ligands (10 CF 3 COO − ).To clearly i l lustrate the interfacial binding profiles and silver arrangements, we describe the structure of Ag102 from the kernel outward.The first hierarchy contains two Ag 10 rings at the upper and lower faces and 10 t BuPhS − coordinated to silver atoms via the μ 4 coordination pattern (Fig. 3 a, b).Namely, the Ag 10 ring of the first hierarchy ligates with the Ag 20 dodecahedron of the Ag 32 kernel to form five vertex-sharing Ag 4 tetragons.The second hierarchy is composed of two Ag 15 rings and 20 t BuPhS − ligands, with the t BuPhS − ligands connecting the inner Ag 10 and Ag 15 rings in μ 3 and μ 4 coordination modes (Fig. 3 c, d).The cyclic (KPO 4 ) 10 acts as not only the anion passivation layer to impede further growth of the inner Ag 32 kernel but also the anionic template to support the outer Ag 70 shell ( Fig. S9).As the outermost silver layer, the third hierarchy consists of an Ag 20 ring at the equator and 30 t BuPhS − ligands arranged in alternating μ 3 and μ 4 coordination modes (Fig. 3 e, f).Interestingly, the t BuPhS − ligands coordinate with the distorted Ag 4 square, which can be seen as a transition from the conventional S-Ag 4 square to the S-Ag 3 triangle.Finally, the fourth hierarchy consists of 10 CF 3 COO − in μ 2 -κ 1 : κ 1 coordination pattern as terminator ligands coordinated on the periphery of saucer-shaped Ag102 (Fig. 3 g, h).
Even more strikingly, A g 12 @A g 20 kernel, (KPO 4 ) 10 anion layer, and each of the aforementioned hierarchies exhibit high symmetry.The 10 2 A g atoms can be divided into two categories: an I h symmetric silvery fullerene A g 12 @A g 20 kernel which contains the concentric icosahedral Ag 12 as well as dodecahedral Ag 20 and an Ag 70 shell in a layer-by-layer arrangement (Fig. 4 a).After passivation by (KPO 4 ) 10 , the symmetry transitions from I h symmetry in A g 12 @A g 20 to D 5d symmetry in A g 12 @A g 20 @(KPO 4 ) 10 .The peripheral 70 Ag atoms are distributed in concentric circles, with the two Ag 10 rings (blue) in the first layer, the two Ag 15 rings (green) in the second layer and a large silver ring of Ag 20 (modena) in the outermost layer.Each Ag 10 ring and Ag 15 ring are parallel to each other but rotated by 36.5 o (A g2-A g20-A g20'-A g14) and 36.8 o (A g15-A g20-A g20'-A g3), respectively ( Fig. S10).The adjacent silver rings and the inner kernel are connected by t BuPhS − ligands.Moreover, the t BuPhS − ligands on each side of the top and bottom of the Ag102 surface together with K + ions show a total of eight pentagonal patterns (Fig. 4 b).This may be related to the fact that they initially

Density functional theory calculation
The room temperature UV-Vis absorption spectrum of Ag102 crystals dissolved in DMF exhibits three absorption bands at 354 nm, 405 nm and 521 nm within the 330 to 800 nm range (Fig. 5 a).In order to unveil the electronic structure of Ag102 , density functional theory (DFT) calculations were performed ( Fig. S15).The calculated time-dependent DFT plus tight binding (TDDFT + TB) spectrum shows good agreement with the experimental spectrum when a constant shift of 0.5 eV is applied to the theoretical spectrum.The shifted calculated optical spectrum (Fig. 5 a) exhibits several peaks, including peaks at 355 nm (peak 1), 398 nm (peak 2) and 488 nm (peak 3), whereas the unshifted spectr um exhibits peak s at ∼400 nm (peak 1), 480 nm (peak 2) and 606 nm (peak 3), respectively.The spectra look almost the same whether water or DMF is used as an implicit solvent in the calculations.GGA functionals often underestimate the energies of excitations, and a shift of 0.5 eV is reasonable to correct the excitation energy results compared with experiments.The DOS (density-of-states) around the Fermi level is shown in Fig. 5 b.For peak 1, peak 2 and peak 3, the major electronic transitions are dominated by the sulfur atomic orbitals to the s and p orbitals of silver atoms.Each broad excitation peak is composed of many different electronic excited states.These three peaks primarily arise from transitions between occupied orbitals that originate from sulfur atomic orbitals into unoccupied orbitals that primarily arise from s and p atomic orbitals on Ag.The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), which are representative of these two types of orbitals, are shown in Fig. 5 c, d.Due to those orbital characters, the main electronic transitions occur with electron density moving from the outer shell to the inner shell and kernel of the system.The UV-Vis absorption spectrum of Ag102 crystals dissolved in trichloromethane is shown in Fig. S16, and the spectrum shows one distinct peak at 478 nm within the same range.
Ag102 exhibits a broad absorption spanning the UV and NIR regions in the solid state ( Fig. S21) and is free of luminescence, suggesting that non-radiative migration is the main route of energy release, so we further investigated the photothermal conversion of Ag102 in the solid state [56 ,57 ].The temperature of Ag102 in the solid state increased from 20 to 301°C in 0.9 s under 450 nm low-power laser irradiation (0.3 W cm −2 ).The temperature increase of Ag102 was 206.1°C (208°C s −1 ) under 660 nm laser irradiation in solid state, while it was 138.5°C (133°C s −1 ) under 808 nm laser irradiation (Fig. 6 c).Although the maximal temperatures of the other laser irradiation wavelengths are lower compared to 450 nm, it sti l l has a fast temperature increase rate.In view of the broad absorption and photothermal conversion properties of Ag102 , we contemplate its potential as a candidate for a remote laser ignition material.A match was used as a model for the remote laser ignition experiment.Prior to the laser ignition tests, we dispersed 2 mg Ag102 in ethanol, applied it evenly to the match head, and then left it for ∼2 h to allow the ethanol to evaporate.The as-obtained sample is hereafter referred to as Ag102 /match.The laser ignition threshold power and ignition time of match and Ag102 /match were measured by changing the laser intensity at a fixed distance of 20 cm.The temperature evolution of the sample over time was recorded using a thermal imaging camera (range: 0-650°C).As shown in Fig. S22, match a nd Ag102 /match were irradiated under three different wavelengths of laser (450, 660 and 808 nm) with the power densities of 0.2-0.6W cm −2 .Notably, under 450 nm laser irradiation, the match could not be ignited at 0.2 W cm −2 , whereas Ag102 /match was ignited within 2.2 s, and as the power density increased to 0.6 W cm −2 , the ignition time of Ag102 /match was further reduced to 0.2 s (Fig. 6 e).When subjected to 660 nm laser irradiation, the match can be ignited until the power density increases to 0.4 W cm −2 with an ignition time of 128 s (Fig. 6 e).In contrast, Ag102 /match can be ignited within the range of 0.2 to 0.6 W cm −2 , with an ignition time reduced to 1.8 s at 0.4 W cm −2 .Furthermore, when exposed to 808 nm laser irradiation, the match can only be ignited when the power density increases to 0.6 W cm −2 , necessitating 31.6 s for ignition.In the range of power densities between 0.2 and 0.6 W cm −2 , Ag102 /match can be ignited and the ignition time decreases from 16.9 to 3.3 s (Fig. 6 e).Coating Ag102 on the surface of the match shortened the ignition time and decreased the laser ignition threshold power.In addition, Ag102 /match has the shortest ignition time under 450 nm laser irradiation, which is related to its strong absorption and better photothermal conversion performance at 450 nm.These results suggest that Ag102 shows significant promise as a photo-responsive material for further applications in remote laser ignition, which is also very important for the development of laser initiators with low initiation energy in the future.

Unraveling the electronic dynamics of Ag102
Whether phonon-assisted non-radiative decay or surface plasmon resonance (SPR) dominates the pathway of photothermal conversion of silver clusters such as Ag102 is an enduring question [58 -60 ].
Herein, femtosecond transient absorption (fs-TA) measurements were performed to probe the electronic dynamics of Ag102 .Upon excitation with a 400 nm laser pulse, rich electronic dynamics can be observed within the 7 ns time window, and an apparent ground-state bleaching (GSB) signal near 500 nm can be identified in the fs-TA spectrum, corresponding to the absorption band of Ag102 , along with a net excited-state absorption (ESA) signal ∼626 nm in the visible range (Fig. 7 a and b).Specifically, the analysis of dynamics traces of 626 nm ESA gives three decay components ( τ 1 = 383.3fs, τ 2 = 4.613 ps and τ 3 = 48.67 ps) (Fig. 7 c), in which the 383.3 fs component should be assigned to the internal conversion (IC) from S n to S 1 state [61 ,62 ], and subsequent picosecond component 4.613 ps may be attributed to structural relaxation within the large cluster.Combined with the long-lived GSB signal in the whole 7 ns time-window, this component may correspond to the relaxation of the excited state electrons from T 1 to S 0 , indicating the existence of a triplet excited state (Fig. 7 d).Owing to the small energy gap in Ag102 , another picosecond component 48.67 ps could be the electron relaxation from S 1 to the ground state ( S 0 ).Moreover, the excitation-pulse-energy-dependent kinetics were investigated using TA measurements (Fig. dynamics.Similar to the reported case of Ag 146 [62 ], the geometry of Ag102 resembles a flying saucer, and the anisotropic shape affects the emergence of SPR, delaying the onset of metallic behavior.Besides, the simplified Jablonski diagram provides basic insights into the preferable mechanism of energy release subsequent to the excitation of Ag102 [66 ,67 ], and it shows that non-fluorescent emitters are complemented by energy decay in the form of heat deexcitation, enabling Ag102 to be employed as excellent photothermal conversion reagents (Fig. 7 f).

DISCUSSION
In summary, we have successf ully sy nthesized a giant 102-nuclei silver NC with a si lvery ful lerene kernel by a DMF-thermal reaction.The silvery fullerene kernel of Ag 32 was trapped by a robust anionic layer of (KPO 4 ) 10 , which plays an important role in passivating the inner Ag 32 kernel and supporting the outer Ag 70 shell.Combined with the t BuPhS − and CF 3 COO − ligands for regioselective distribution on the surface of the Ag102 , the whole cluster possesses a D 5 d symmetry.Ag102 exhibits superior photothermal conversion performance in both solution and crystalline states, and the photothermal conversion efficiency of Ag102 solution at 450 nm is remarkably high up to 67.1% ± 0.9%.Furthermore, fs-TA studies have substantiated the molecule-like characteristics of Ag102 , and its photothermal conversion is attributed to non-radiative transitions.Our study provides a cornerstone for further incorporating M into coinage metal NCs, and the fullerene topologic structure of Ag 32 trapped in silver NC will open up new opportunities for the synthesis of more silvery fullerenes.

Figure 5 .
Figure 5. (a) Experimental and calculated UV-Vis absorption spectra of Ag102 , and the experimental UV-Vis absorption spectrum of Ag102 recorded in DMF solution at room temperature.(b) DOS around the Fermi level of the Ag102 ; the arrow indicates the dominant transitions for the three excitation peaks.(c) HOMO and (d) LUMO for the Ag102 system (isovalue = 0.01 au).Color labels: purple, Ag; cyan, K; orange, P; blue, N; yellow, S; gray, C; red, O; white, H.

Figure 6 .
Figure 6.Photothermal conversion curves (a), photothermal heating and cooling cycles (b) and thermal images (d) of the CHCl 3 solution of Ag102 at the concentration of 100 μM under 450, 660 and 808 nm laser irradiation (0.3 W cm −2 ).(c) Photothermal conversion curves of Ag102 in the solid state under 450, 660 and 808 nm laser irradiation (0.3 W cm −2 ).Insets: thermal images of Ag102 at the highest temperature.(e) The comparison of the ignition time of match and Ag102 /match at different laser power densities at wavelengths of 450, 660 and 808 nm, respectively.The numbers in the figure represent the ignition time (seconds), the cross means it cannot be ignited.The error bars in Fig. 6 d were determined from the standard deviation of three parallel experiments.

Figure 7 .
Figure 7. fs-TA characterization of the Ag102 .(a) Transient absorption data map pumped at 400 nm.(b) The TA spectra of Ag102 at different time delays.(c) Kinetic traces probed at 626 nm.(d) Kinetic traces at 541 nm and the corresponding fitting.(e) Excitation pulse energy dependent kinetics.(f) Simplified Jablonski diagram illustrating photophysical processes of Ag102 at room temperature.IC: internal conversion, ISC: intersystem crossing.
Experimental details, computational details, detailed crystallographic structure and data including the CIF file, PXRD and IR are available within the article and its Supplementary information files.Other relevant data are available from the corresponding author upon request.The X-ray crystallographic coordinates for structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition number CCDC 2323089 for Ag102 .These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_ request/cif.were supported by the National Science Foundation (CHE-1905048) of the United States.The computing for this work was performed on the Beocat Research Cluster at Kansas State University, which is funded in part by NSF grants CHE-1726332, CNS-1006860, EPS-1006860, and EPS-0 9194 43.