Cluster Compounds |Very Important Paper |

Silver Thiolate Nano-sized Molecular Clusters and TheirSupramolecular Covalent Frameworks: An Approach TowardPre-templated Synthesis

Zi-Yi Chen+, Dennis Y. S. Tam+, Leon Li-Min Zhang, and Thomas C. W. Mak*[a]

Dedicated to the memory of Prof. Wai-Kee Li (1942–2016)

Abstract: A series of seven new complexes including silver-

thiolate molecular clusters and their covalent supramolecularframeworks have been assembled from the silver carbide

precursor Ag2C2 using a C22@ pre-templated approach.

Herein, two prototype clusters Ag14(SR)6 and CO3@Agm(SR)10

(R = isopropyl, cyclohexyl or tert-butyl ; m = 18 or 20) are em-

ployed to construct cluster-based metal–organic frameworksof different dimensions. In particular, both new ellipsoidal

tetradecanuclear molecular cluster compounds, namely,Ag14(S-iPr)6(CO2CF3)8·(DMSO)6 (two polymorphic forms1, 2) and [Ag14(S-Cy)6(CO2CF3)8(DMSO)4]·(DMSO)3 (3),and a cluster-based metal–organic framework {Ag3[Ag14(S-

iPr)6(CO2CF3)11(H2O)3CH3OH]·(H2O)2.5}n (4) have been isolatedand structurally characterized. Furthermore, increased acidity

of the reaction mixture afforded three carboxylate-templated

cluster based frameworks: a chain-like compound{[HN(CH3)2CO]·[CO3@Ag18(S-tBu)10(NO3)7(DMF)4]·DMF}n (5), as

well as two layer-type compounds, namely, {Ag[CO3@Ag20(S-iPr)10(CO2CF3)9(CO2HCF3)(CH3OH)2]}n (6) and {Ag2[CO3@Ag20(S-

Cy)10(CO2CF3)10(CO2HCF3)2(H2O)2]·(H2O)3·(CH3OH)3}n (7) exhibit-

ing sql-net characteristics. It is demonstrated that the C/C2@

pre-template, which draws several Ag+ ions together to

form the C2@Agn entity, plays an indispensable role in thesyntheses of these compounds. Furthermore, covalent link-age of these nano-sized silver thiolate clusters from one- tothree-dimensions revealed enormous potential for the futuredevelopment of silver cluster-based frameworks.

Introduction

The synthesis and characterization of metal cluster compoundsis an active frontier in contemporary chemistry owing to its im-portance in fundamental science with appealing applications

in catalysis, sensors and luminescence materials.[1] Molecularclusters are of particular interest not only because of their richchemistry when they act as discrete well-defined ‘macromole-cules’ but also as nano-sized building blocks in the assembly

of ordered super-structured materials.[2] Among them, cluster-based metal–organic frameworks constitute a class of promis-

ing crystalline solids which benefit from the cluster buildingblock synthetic approach.[3] Compared with single metal-ionbased MOFs, ‘cluster nodes’ of bigger size and more linking

sites endow the cluster-based MOFs with highly connectednets, large channels as well as enhanced stability. Pursing the

prototype molecular building cluster of cluster-based MOFs isa critical issue, as it provides unambiguous and valuable infor-

mation about the formation route and mechanism of the clus-ter-based MOF, which counteracts the argument that the clus-

ter node is merely a “pseudo-entity” to facilitate the elabora-

tion and understanding of the structure.[4] However, the isola-tion and crystallographic characterization of both molecularcluster building unit and the corresponding MOF proved to bedifficult as only a few successful examples have been reported

to date.[5]

In the case of coinage-metal cluster compounds, relatively

strong metallophilic interactions between closed-shell d10

metal centers facilitate the consolidation of individual clusters,which may provide additional benefits in identifying the mo-

lecular cluster building unit.[6] Moreover, several cluster-basedAgI- or AuI-organic frameworks have been successfully con-

structed by employing different strategies such as “clusterlinker approach”,[5a] “large cluster and small bridge”,[7] as well

as cooperating with ancillary bridging ligands such as 4,4’-bi-

pyridine.[8]

Our previous contribution in this area has been mainly cen-

tered on the construction of silver(I) cluster compounds bear-ing ethynide RC/C@ and acetylenediide (IUPAC name ethyne-

diide) C/C2@ ligands.[9] The sustained effort allowed us to buildan extensive library of crystallography-characterized silver car-

[a] Dr. Z.-Y. Chen,+ D. Y. S. Tam,+ Dr. L. L.-M. Zhang, Prof. Dr. T. C. W. MakDepartment of Chemistry and Center of Novel Functional MoleculesThe Chinese University of Hong KongShatin, New Territories Hong Kong SAR (People’s Republic of China)E-mail : tcwmak@cuhk.edu.hk

[++] These authors contributed equally to this work.

Supporting information and the ORCID identification number(s) for the au-thor(s) of this article can be found under https ://doi.org/10.1002/asia.201701150.

Chem. Asian J. 2017, 12, 2763 – 2769 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim2763

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bido cluster compounds, from which the supramolecular syn-thon C2@Agn (n = 6–10) has been demonstrated to be a com-

monly-occurring structure-building unit.[10] The initial goal ofour effort was to incorporate C2

2@ as an anion template with

thiolate ligands to construct silver chalcogenolate clusters,which proved to be unsuccessful. However, while using Ag2C2

as a reaction precursor, the synthetic effort yielded a series ofseven new complexes including molecular silver-thiolate clus-ters and their covalent frameworks of different dimensionalities

(Scheme 1), in which the C22@ species may play the role of a

pre-template in the assembly process. Firstly, both new ellipsoi-dal tetradecanuclear molecular cluster compounds Ag14(S-

iPr)6(CO2CF3)8·(DMSO)6 (polymorphic forms 1 and 2) and[Ag14(S-Cy)6(CO2CF3)8(DMSO)4]·(DMSO)3 (3), and the MOF

{Ag3[Ag14(S-iPr)6(CO2CF3)11(H2O)3CH3OH]·(H2O)2.5}n (4) havebeen isolated and structurally characterized. Next,

a disk-like anion-templated cluster CO3@Agm(SR)10 was

assembled into a chain-like compound{[HN(CH3)2CO]·[CO3@Ag18(S-tBu)10(NO3)7(DMF)4]·DMF}n (5) as

well as two layer-type compounds{Ag[CO3@Ag20(S-iPr)10(CO2CF3)9(CO2H CF3)(CH3OH2)2]}n (6) and

{Ag2[CO3@Ag20(S-Cy)10(CO2CF3)10(CO2HCF3)2(H2O)2]·(H2O)3

·(CH3OH)3}n (7).

Results and Discussion

General remarks of the synthesis

As shown in Scheme 1, at high concentration of Ag+ , dissolu-tion of polymeric silver carbide Ag2C2 resulted in generation of

C2@Agn moieties consolidated by argentophilic interactions.Further addition of silver thiolate salt (Ag-SiPr or Ag-SCy) ledto isolation of Ag14S6 cluster-based compounds. When the

strong donating solvent DMSO is used in synthesis and crystal-lization, the cluster more likely retains its molecular form in

forming compound 1–3, which are ligated by trifluoroacetateand DMSO ligands. Using methanol as solvent, the DMSO mol-

ecules occupying ‘free’ coordinating sites of the above clusters

are replaced by trifluoroacetate ligands in linking adjacentclusters to form 3D-net cluster-based MOF 4. Meanwhile, treat-

ing the C2@Agn species directly with excess amount of thiolsyielded different cluster-based frameworks 5–7, which contain

the CO32@ templated cluster core CO3@Agn(SR)10. The fixation

of carbon dioxide from the air, which led to CO32@ that func-

tions as a template in cluster assembly, has been reported inseveral papers in the literature.[11] While the completely differ-

ent roles played by silver thiolate salt and thiol as reactantsmerit discussion, it is most likely that the acidity of solution

played a vital role in the synthesis, as compounds 5–7 all haveprotonated ligands. From our experiments, more acidic reac-

tion mixtures took much longer time to afford crystals, whichis consistent with equilibrium shift of the thiolates and thiols

to thiols. The longer time is required for the reaction mixture

to capture enough atmospheric dioxide carbon for final prod-uct formation.

Description of crystal structures

Ag14(S-iPr)6(CO2CF3)8·(DMSO)6 (1, 2) and [Ag14(S-Cy)6-

(CO2CF3)8(DMSO)4]·(DMSO)3 (3). Single-crystal diffraction analy-sis reveals that compound 1 crystallizing in the monoclinic

space group P21/n features a neutral centrosymmetric ellipsoi-

dal cluster containing 14 silver(I) ions, six 2-propanethiolate li-gands, eight trifluoroacetate ligands and six dimethyl sulfoxide

ligands (Figure 1 a). Each 2-propanethiolate ligand coordinatesto a Ag4 trapezoid or a Ag4 square in a m4 mode with Ag···S

bonds length ranging from 2.438 to 2.539 a. By sharing verti-ces with each other, the Ag4 trapezoids and squares are linked

together to form a hollow ellipsoidal Ag14S6 cage, which exhib-

its a Ag3-Ag8-Ag3 (triangle-octagon-triangle) three-layer skeletalarrangement (Figure 1 b and 1 c).

It is worth noting that the Ag···Ag distances ranging from2.881 to 3.310 a indicate that there are significant argentophil-

ic interactions in consolidating the cluster. Each of the eightperipheral trifluoroacetate ligands adopts either a m2-h1,h1 coor-

Scheme 1. Pre-templated syntheses of compounds 1–7.

Figure 1. (a) Perspective view of the molecular clusterAg14(S-iPr)6(CO2CF3)8·(DMSO)6 (1). Top (b) and side (c) view of the ellipsoidalAg14S6 core and the three-layer arrangement. Color code: Ag: blue, pink andcyan; S: yellow; O: red; F: green; C: gray. The colorless ball is used to showthe inner cavity of the Ag14S6 core.

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dination mode in bridging two adjacent silver(I) ions or a m2-h2,h1 mode in capping a Ag3 triangle, and each of the six

DMSO ligands links two silver ions. The Ag···O bond lengths ofthis cluster range from 2.225 to 2.528 a. Furthermore, neigh-

boring silver(I) thiolate clusters in 1 are interconnected by in-termolecular hydrogen bonds CH(thiolate)···F(trifluoroacetate) in a body-centered packing mode. Complex 2 belonging to triclinicspace group P(1 has the same cluster structure with 1 but themolecules are packed in a different manner (Figure S1).

Cyclohexyl thiolate-capped cluster compound 3 also crystal-lizing in the space group P(1 features a similar Ag14S6 clusterunit, but it differs from that in 1 in two respects. First, the mo-lecular skeleton of this Ag14S6 unit is somewhat shrunk and dis-

torted. Particularly, two opposite corner silver(I) atoms shifttoward the cluster center, enabling two cyclohexyl thiolates li-

gands to adopt a m5 mode, in contrast to the m4 mode adopted

by the 2-propanethiolate ligand in 1 and 2. Second, thenumber of ligated DMOS molecules decreases from six to four

(Figure S2). Clearly, these differences stem from the largersteric bulk of the cyclohexyl group, which squeezes out two

DMSO molecules from the outer coordination-sphere of thecluster.

{Ag3[Ag14(S-iPr)6(CO2CF3)11(H2O)3CH3OH]·(H2O)2.5}n (4). Com-

plex 4 crystallizing in the orthorhombic space group Pccn ex-hibits a covalent 3D metal–organic framework utilizing the

Ag14S6 cluster as its building block. In the cluster unit, the m2

DMSO molecules in previous compounds 1–2 are now re-

placed by m3- or m4-trifluoroacetate ligands, which connecteach Ag14S6 cluster to six isolated silver(I) ions (Figure 2 a). Each

of these silver(I) ion serves as a linear linker to connect two ad-

jacent clusters, as shown in Figure 2 b, such that each Ag14S6

cluster is hexa-linked with six identical neighbors in a distortedoctahedral manner. Therefore, a convoluted 3D net with single

6- connected node was obtained (Figure 2 c).To gain further insight into the net topology, we analyzed it

using the TOPOS software.[12] The result revealed that the unin-odal net features an unprecedented topology described by the

Schl-fli symbol {4^7.6^8}. Notably, the nano-sized Ag14S6

based-building block allows for connectivity in a rather flexibleand asymmetrical fashion which may lead to manifestation of

the new topology, with adjacent clusters separated by distan-ces ranging from 14.0 a to 15.2 a. The existence of a molecularcluster structure and clustered-based framework topology in 4provides strong evidence that the assembly proceeds in astep-by-step manner: that is, from generation of molecularclusters to their condensation into a crystalline framework.

{[HN(CH3)2CO]·[CO3@Ag18(S-tBu)10(NO3)7(DMF)4]·DMF}n (5).

Compound 5 crystallizing in space group P(1 features a cova-lent linear assembly of carboxylate-templated Ag18S10 clusters.

With a carboxylate group occupying its center, the centrosym-metric disk-like cluster of 5 is composed of eighteen silver

ions, ten tert-butyl thiolate ligands, six nitrate ions and four di-methylformamide molecules (Figure 3 a). As seen from Fig-

ure 3 b and 3 c, the Ag18 cluster can be divided into three

layers denoted as Ag5 (a pentagon), Ag8 (an octagon) and Ag5

(a pentagon). Eight of the ten thiolate ligands each adopt them4 mode to coordinate an Ag4 tetragon, while the other two

each adopt the m3 mode to coordinate an Ag3 triangle. TheAg···S bond lengths ranging from 2.369 to 2.877 a are compa-

rable to those reported for silver thiolate clusters. The six ni-trate ions function either as monodentate m-kO : kO’ ligands or

bridging m2-kO : kO’ ligands. All dimethylformamide ligands

serve as mono-coordinate terminal ligands. The carboxylateligand adopts a m8-h2, h3, h3 mode in liking two Ag5 pentagons.

Inter-cluster connection is provided by a m3-h1, h2 nitrate toform an infinite linear chain (Figure 3 d).

{Ag[CO3@Ag20(S-iPr)10(CO2CF3)9(CO2HCF3)(CH3OH)2]}n (6)and {Ag2[CO3@Ag20(S-Cy)10(CO2CF3)10(CO2HCF3)2(H2O)2]·(H2O)3

Figure 3. (a) Perspective view of the molecular cluster building unit[CO3@Ag18(S-tBu)10(NO3)6(DMF)4] in 5. Panels (b) and (c) show top and sideviews, respectively, of the disk-like Ag18S10 core and its three-layer arrange-ment. (d) Linear linkage of Ag18S10 cluster units by nitrate ligands. Colorcode: Ag: blue, cyan and pink; S: yellow; O: red; C: gray; N: green.

Figure 2. (a) Perspective view of the molecular cluster-based building blockAg14(S-iPr)6 with its six linking sites in the crystal structure of{Ag3[Ag14(S-iPr)6(CO2CF3)11(H2O)3CH3OH]·(H2O)2.5}n 4. Ball-and-stick (b) andspace-filling (c) diagrams showing the spatial arrangement of a center clus-ter surrounded by six adjacent clusters. (d) Three-dimensional uninodal 6-connected net of 4, with each Ag12S6 cluster represented by a sky-bluenode. Color codes for atoms: Ag: blue, cyan and green; S: yellow; O: red; C:gray.

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·(CH3OH)3}n (7). Complexes 6 and 7 crystallize in monoclinicspace groups C2/c and P21/c, respectively. Each of them con-

tains a 2D open framework utilizing the CO3@Ag20S10 cluster asa structure-building unit. Similar CO3@Ag20S10 molecular skele-

tons have been reported in the literature,[13] while our com-pounds are characteristic by the incorporation of cyclohexyl

thiolate ligands and trifluoroacetate ligands. In each com-pound, the molecular cluster is quadruply connected withequivalent neighbors to form a layer structure with 4,4-net

topology. As shown in Figure 4 a, there are two types of ‘arms’between neighbor clusters in 6. Type-A refers to direct linkage

between two neighbor clusters by trifluoroacetate ligands, andin this type, adjacent clusters are separated by 14 a. Type-B

makes use of an isolated silver atom to bridge two clusters,where the distance between adjacent clusters is longer at

17 a. In contrast, all inter-cluster linkages in 7 belong to TypeB. These differences could be plausibly explained by the factthat the bulkier cyclohexyl group in 7 hinders direct linkage ofadjacent clusters, and thus two types of (4,4) nets are manifest-ed (Figure 4 b).

Comparative study of Ag12S6, Ag14S6, Ag18S10 and Ag20S10

clusters

Most recently, Zang and co-authors reported two silver chal-cogenate clusters Ag12(SCH2C10H7)6(CO2CF3)6(CH3CN)6 and

Ag12(S-tBu)6(CO2CF3)6(CH3CN)6[14] that feature the Ag12S6 molec-

ular skeleton, and their Ag12 component can be divided into

three layers, that is, Ag3-Ag6-Ag3, as shown in Figure 5 a. How-ever, in our experiment, the use of similar reactants led to the

isolation of Ag14S6 clusters (1–4), which exhibit the same Ag3-

Ag8-Ag3 arrangement (Figure 5 b). A similar phenomenon wasfound in the present carboxylate-templated CO3@Ag18S10 and

CO3@Ag20S10 central units, which adopt Ag5-Ag8-Ag5 (Figure 5 c)and Ag5-Ag10-Ag5 (Figure 5 d) configurations, respectively. For

Ag12S6 and Ag14S6, we believe that the driving force for the dif-ferentiation is the concentration of Ag+ . The high concentra-

tion of Ag+ is more likely to facilitate the onset of argentophil-ic interactions, so that formation of silver-rich Ag14S6 clusters

may be favored. This rationale is supported by the crystalstructure of 1 in which considerable numbers of very short Ag-

Ag contacts are observed. It is quite plausible that C2@Agn

plays an indispensable role in forming the Ag14S6 cluster. Other

factors such as employment of different R groups and reaction

solvents may also have some contributions. Structural correla-tion of the molecular skeletons of silver thiolate clusters of in-

creasing nuclearity is shown in Figure 5.The successful isolation of a family of four analogous silver

thiolate clusters strongly indicates that molecular dynamics op-erate in the cluster assembly processes. The clusters may un-

dergo association–dissociation processes, which enables them

to change their components and geometries in adaptation tothe reaction environment (concentration of Ag+ , acidity, the

template). In this regard, the terms “constitutional dynamicchemistry” and “adaptive chemistry” proposed by Lehn may be

applicable.[15]

Photoluminescence study of compound 6

The solid-state photoluminescence property of compound 6has been investigated at room temperature. As shown inFigure 6, compound 6 exhibits dual emissions with variable in-

tensity depending on the excitation wavelength. Upon 260 nmexcitation, compound 6 emits a weak emission centered at

403 nm and a relatively stronger emission centered at 553 nm.

While the intensity of the low-energy emission increases mar-ginally upon changing the excitation wavelength from 270 to

260 nm, an eight-fold increase was observed for the high-energy emission. In this regard, it is understandable that an in-

crease in excitation energy leads to intensity enhancement ofthe high-energy emission. The lifetimes of the low- and high-

Figure 5. Top views of the molecular skeletons of silver thiolate clusters.(a) Ag12S6 in Ag12(SCH2C10H7)6(CO2CF3)6(CH3CN)6, (b) Ag14S6 in 1–4, (c) Ag18S10

in 5 and (d) Ag20S10 in 6 and 7. Color code: Ag: blue, cyan and pink; S:yellow.

Figure 4. (a) The molecular building block in 6 with its four linking sites, andcondensation of blocks into a 4,4-net. (b) Similar condensation of molecularbuilding blocks in 7. Note the difference between the 14 a (orange) and17 a (cyan) ‘arms’. Color code: Ag: blue and cyan; S: yellow; O: red; C: gray;F: green.

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energy emission bands were measured to be 109 and 45 ms,

respectively, suggesting the triplet parentage of their emissionorigin. With reference to reported luminescent silver thiolate

complexes,[7, 13, 14] the emission origin could be tentatively as-cribed to ligand-to-metal charge transfer (S!Ag) with a CC

(cluster-centred) triplet excited state that has been modifiedby argentophilic interactions. Nevertheless, it is notable that

while the 2D assembly of compound 6 features dual-emission,

the previously reported discrete cluster [Ag20(S-tBu)10-(CO2CF3)2]Cl·(CO2CF3)7·5 CH3OH emits a single emission band at

410 nm,[16] and the 1D assembly of {[(CO32@)@Ag20(S-

tBu)10(CH3COO)8(DMF)2]·2 H2O}n shows a broad emission spread-

ing from 400 to 600 nm.[13] The results demonstrate that the lu-minescence behavior of silver thiolate cluster compounds isstrongly structure-dependent where minor variation, such as

dimensionality of molecular assembly, can cause significant dif-ference on their photoluminescence properties.

Conclusions

A series of seven new complexes including molecular silver-thi-

olate clusters and their covalent supramolecular frameworkshave been assembled from a silver carbide precursor (Ag2C2)using a pre-templated approach. The new Ag14S6 building unit

found in ellipsoidal tetradecanuclear molecular cluster com-pounds 1–3 was installed into a three-dimensional net-like

framework, namely, {Ag3[Ag14(S-iPr)6(CO2CF3)11(H2O)3CH3OH]-·(H2O)2.5}n (4), which utilized the linkage of silver trifluoroace-

tate units to form a 3D net featuring an unprecedented unim-

odal 6- connected topology. Increased acidity of the reactionmixture afforded three carboxylate-templated cluster-based

frameworks: one-dimensional structure 5 as well as two layer-type compounds 6 and 7 with 4,4-net characteristics.

A comparative study of the molecular skeletons of Ag12S6,Ag14S6, Ag18S10 and Ag20S10 indicates that the pre-template

ethynediide C/C2@, which draws several Ag+ ions together toform the C2@Agn entity, plays an indispensable role in the syn-

theses of Ag14 cluster compounds. The present report alsosheds some light on the “constitutional dynamic chemistry”

and “adaptive chemistry” of this complex system. Furthermore,the one- to three-dimensional covalent assemblies of these

nano-sized silver thiolate clusters reveal an enormous potentialfor future development of silver cluster-based frameworks.

Experimental Section

General Remarks

All chemicals and solvents obtained from commercial sources wereof analytically pure grade and used without further purification.Polymeric [Ag2C2]n was prepared according to a literature proce-dure.[17] Like some of the silver complexes, complexes 1–7 are sen-sitive to light as the single crystals become blackish within oneweek when exposed to ambient light. Therefore, photolumines-cence measurements were conducted on freshly prepared samplesusing a Edinburgh FLS980 Fluorescence Spectrometer. These silverthiolate complexes also show low thermal stability as they turnedblack upon gentle heating (&40 8C). Caution: Anhydrous Ag2C2 ishighly explosive, and a freshly prepared sample should never be air-dried, heated, or kept for a prolonged period. Only a milligram quan-tity should be used in any chemical reaction.

Synthesis of 1

Polymeric complex [Ag2C2]n (30 mg) and AgCO2CF3 (220 mg,1 mmol) were dissolved in DMSO (1 mL), and Ag-SiPr (10 mg) wassubsequently added to the solution. The mixture was allowed tostir until all solids dissolved. The solution was then filtered and thefiltrate was transferred to a test tube. After carefully layering 3 mLdeionized water onto the filtrate, yellow block crystals of 1 wereobtained within one week in the dark in a yield of ca. &25 %(based on Ag-SiPr).

Synthesis of 2

The synthetic procedure is similar to that of 1 except that thedouble amount of AgCO2CF3 (440 mg, 2 mmol) was used. Yellowblock crystals of 2 were obtained in a yield of ca. &20 % (based onAg-SiPr).

Synthesis of 3

The synthetic procedure is similar to that of 1 except that Ag-SCy(10 mg) was used instead of Ag-SiPr. Yellow block crystals of 3were obtained in a yield of ca. &20 % (based on Ag-SCy).

Synthesis of 4

Polymeric [Ag2C2]n (30 mg), AgCO2CF3 (440 mg, 2 mmol) and AgBF4

(191 mg, 1 mmol) were firstly dissolved in methanol (1.5 mL) anddeionized water (0.5 mL). Subsequently, Ag-SiPr (20 mg) was addedto the solution. After stirring for about 30 min, the solution was fil-tered and left to stand in the dark at room temperature. Colorlessblock crystals of 4 were obtained by slow evaporation the motherliquid in five days in a yield of ca. &10 % (based on Ag-SiPr).

Figure 6. Solid-state emission spectra of 6 at 298 K under different excitationwavelengths.

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Synthesis of 5

Polymeric complex [Ag2C2]n (30 mg) and AgNO3 (220 mg) were dis-solved in DMF (1 mL), and tert-butylthiol (0.1 mL) was subsequentlyadded to the solution. The mixture was allowed to stir until allsolids dissolved. The solution was then filtered and the filtrate wastransferred to a test tube. Yellow block crystals of 5 were obtainedwithin one week by vapor diffusion of Et2O into its mother liquidin the dark to furnish a yield of about 15 % (based on tert-butylth-iol).

Synthesis of 6

The synthetic procedure is similar to that of 4 except that 2-pro-panethiol (0.1 mL) was used instead of Ag-SiPr. Colorless blockcrystals of 6 were obtained in a yield of ca. &10 % (based on 2-pro-panethiol).

Synthesis of 7

The synthetic procedure is similar to that of 4 except that cyclo-hexanethiol (0.1 mL) was used instead of Ag-SiPr. Colorless blockcrystals of 7 were obtained in a yield of ca. &10 % (based on cyclo-hexanethiol).

X-ray crystallography

Crystal data were collected on a Bruker Smart Apex II CCD diffrac-tometer with MoKa radiation (l= 0.71073 a) at 173(2) K. The inten-sities were corrected for Lorentz and polarization factors, as well asfor absorption by the multi-scan method. The structure was solvedby the direct method and refined by full-matrix least-squares fit-ting on F2 with the ShelXS and ShelXL programs within the Olex2suite. CCDC 1565943–1565949 contain the supplementary crystallo-graphic data 1–7 for this paper. These data can be obtained freeof charge from The Cambridge Crystallographic Data Centre.

Crystal Data for 1: C46H66Ag14F24O22S12 ; monoclinic; P21/n ; a =13.8969(9), b = 14.1770(10), c = 24.1230(17) a; b= 97.1240(10)8 ; V =4715.9(6) a3 ; Z = 2; 71 740 reflections collected; 8540 independentreflections; 0 restraints; 535 parameters; R1 = 0.0799 [I>2s(I)] ;wR2 = 0.2193 (all data).

Crystal Data for 2: C46H78Ag14F24O22S12 ; triclinic; P-1; a =15.4937(12), b = 16.3654(12), c = 18.9480(14) a; a= 92.009(2), b=97.1240(10), g= 91.6630(10)8 ; V = 4655.0(6) a3 ; Z = 2; 54 064 reflec-tions collected; 16 798 independent reflections; 0 restraints;1097 parameters; R1 = 0.1030 [I>2s(I)] ; wR2 = 0.2697 (all data).

Crystal Data for 3: C63Ag14F24O22S12 ; triclinic; P-1; a = 15.1933(7),b = 15.5821(7), c = 25.0839(11) a; a= 86.880(2), b= 89.240(2), g=69.675(2)8 ; V = 5560.4(4) a3 ; Z = 2; 98 408 reflections collected;26 649 independent reflections; 28 restraints; 656 parameters; R1 =0.0860 [I>2s(I)] ; wR2 = 0.2867 (all data).

Crystal Data for 4: C82Ag34F66O57S12 ; orthorhombic; Pccn ; a =24.0242(19), b = 32.073(3), c = 22.3790(18) a; V = 17 244(2) a3 ; Z = 4;67 962 reflections collected; 15 593 independent reflections; 46 re-straints; 958 parameters; R1 = 0.1228 [I>2s(I)] ; wR2 = 0.3293 (alldata).

Crystal Data for 5: C59Ag18N13O30S10 ; triclinic; P-1; a = 12.9947(4),b = 14.5700(5), c = 17.0383(5) a; a = 76.432(2), b= 73.870(2), g=64.080(2)8 ; V = 2763.17(16) a3 ; Z = 1; 32 876 reflections collected;12 654 independent reflections; 3 restraints; 592 parameters; R1 =

0.0658 [I>2s(I)] ; wR2 = 0.2164 (all data).

Crystal Data for 6: C53Ag21F30O25S10 ; monoclinic; C2/c ; a =29.5347(15), b = 14.3440(7), c = 24.9005(13) a; b= 100.810(2)o ; V =

10 361.8(9) a3 ; Z = 4; 84 739 reflections collected; 12 402 independ-ent reflections; 0 restraints; 657 parameters; R1 = 0.0353 [I>2s(I)] ;wR2 = 0.1031 (all data).

Crystal Data for 7: C88H110Ag22F36O35S10 ; monoclinic; P21/c ; a =25.2459(11), b = 19.8019(9), c = 28.6920(13) a; b= 908 ; V =14 343.6(11) a3 ; Z = 4; 234 956 reflections collected; 34 466 inde-pendent reflections; 187 restraints; 1460 parameters; R1 = 0.1189[I>2s(I)] ; wR2 = 0.4036 (all data).

Acknowledgements

Financial support by the Wei Lun Foundation and the award ofpostgraduate studentships to Z.-Y. Chen, Dennis Y.-S. Tam and

Leon Li-Min Zhang by The Chinese University of Hong Kong

are gratefully acknowledged.

Conflict of interest

The authors declare no conflict of interest.

Keywords: cluster compounds · metal-organic frameworks ·silver thiolate · supramolecular chemistry · X-raycrystallography

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Manuscript received: August 9, 2017Revised manuscript received: September 11, 2017

Accepted manuscript online: September 15, 2017

Version of record online: September 26, 2017

Chem. Asian J. 2017, 12, 2763 – 2769 www.chemasianj.org T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim2769

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