Structure-Directing Role of Phosphonate in the Synthesis of High

Aug 15, 2017 - For the first time, phosphonate as a structure-directing template is used to build up high-nuclearity silver sulfide-ethynide-thiolate ...
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Structure-Directing Role of Phosphonate in the Synthesis of HighNuclearity Silver(I) Sulfide-Ethynide-Thiolate Clusters Jun-Ling Jin,† Yun-Peng Xie,*,† Han Cui,‡ Guang-Xiong Duan,† Xing Lu,*,† and Thomas C. W. Mak# †

State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology (HUST), Wuhan 430074, China ‡ Dalian Entry-Exit Inspection and Quarantine Bureau, Dalian, China # Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, People’s Republic of China S Supporting Information *

ABSTRACT: Phosphonate ligands as structure-directing components have been employed to construct four new high-nuclearity silver(I) sulfide-ethynide-thiolate clusters, in which silver(I) aggregates tBuCC⊃Ag3, tBuCC⊃Ag4, and 2tBuC C⊃Ag7 are bridged by tBuS− ligands to engender respective silver(I) ethynidethiolate clusters functioning as integral shell components, which are supported by phosphonate ligands. In each silver(I) sulfide-ethynide-thiolate cluster, a different encapsulated silver sulfide cluster serves as a core template.

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INTRODUCTION Metal phosphonates have attracted a great deal of attention due to their interesting structures and potential applications in the field of ion exchange, catalysis, adsorption and separation, proton conductivity, water treatment, biotechnology, photochemistry, dental medicine, cancer treatment, magnetism, and magnetic refrigeration.1 The reactions of phosphonate ligands with metal ions afford products that vary structurally from discrete molecules to multidimensional coordination polymers.2,3 Recently the RCCAg and RSAg (R = alkyl, aryl, heteroaryl) metal−ligand supramolecular synthons have been intensively investigated as novel polynuclear building units to assemble high-nuclearity silver(I) clusters.4−7 The carbon-rich monoanions of the type RCC− is invariably inserted into a pocket that is composed of three-to-six silver(I) centers, which are consolidated by cooperative argentophilic interactions. As to the silver(I) tert-butylethynide complexes, silver triangle, planar, or butterfly silver tetragons are usually found. In contrast, the thiolate ligand generally adopts μ3- or μ4-ligation modes to form Ag3S tetrahedron or Ag4S square pyramid, respectively. In previous studies, we employed phosphonic acid as a precursor to react with RCCAg or RSAg to construct a series of high-nuclearity silver(I) cluster compounds.8 In phosphonate-functionalized silver(I)-ethynide clusters, the phosphonate ligand constitutes a structural component for building up the cluster shell, functions as a tripodal strut to support vertex © XXXX American Chemical Society

sharing or fusion of two small silver(I) clusters to form an enlarged composite cluster,8a−d while the phosphonate ligand can act as a structure-directing template in influencing the formation of silver(I)-thiolate clusters.8e The use of phosphonate provides an effective way to construct novel high-nuclearity silver(I) clusters. Hence new synthetic routes, especially those involving the combined use of RCCAg, RSAg, and phosphonate, are worthy of further exploration because they may lead to the assembly of a novel type of high-nuclearity phosphonate-functionalized silver(I) sulfide-ethynide-thiolate clusters. We have now isolated four unprecedented high-nuclearity clusters with phosphonate-functionalized silver ethynidethiolate cluster units as their surface components, as well as different kinds of silver sulfide cluster cores as their encapsulated templates: {S@Ag 1 2 S 6 @Ag 3 6 ( t BuC C)12(tBuS)12(nBuPO3)2(nBuPO3H)6} (1), {S@Ag12S6@Ag36(tBuCC)12(tBuS)12(tBuPO3)8}{S@Ag16(tBuS)8(CH3OH)2(H2O) 4}·5CH3OH (2), {[(Ag3S3)S3]@Ag42( tBuCC) 12( t BuS) 18 ( n BuPO 3 )( n BuPO 3 H)(NO 3 ) 4 (CH 3 OH) 2 (H 2 O) 2 }· 4[H3O] (3), and {Ag3S3@Ag30(tBuCC)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6(H2O)2} (4). Received: May 26, 2017

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DOI: 10.1021/acs.inorgchem.7b01326 Inorg. Chem. XXXX, XXX, XXX−XXX

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Inorganic Chemistry

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RESULTS AND DISCUSSION Synthesis and Structure of {S@Ag12S6@Ag36(tBuC C)12(tBuS)12(nBuPO3)2(nBuPO3H)6} (1). The reaction of tBuSAg, tBuCCAg, nBuPO3H2, and AgBF4 in methanol/ dichlormethane afforded yellow crystals of {S@Ag12S6@Ag36(tBuCC)12(tBuS)12(nBuPO3)2(nBuPO3H)6} (1). Single-crystal X-ray analysis9 reveals that complex 1 is a Ag48 sulfideethynide-thiolate cluster, whose structure is depicted in Figure 1.

Figure 2. Left: Schematic representations of the assembly of tBuC C⊃Ag3 building units and tert-butylthiolates to produce the [Ag36(tBuCC)12(tBuS)12]12+ shell in 1 under the influence of nbutylphosphonates as structure-directing templates. Right: Topological representation of the giant truncated octahedral geometry of the [Ag36(tBuCC)12(tBuS)12]12+ cluster with {tBuCC⊃Ag3} and tertbutylthiolates as connecting nodes. Eight hexagonal faces each capped by a n-butylphosphonate.

butylthiolates, resulting in a silver(I) ethynide-thiolate cluster exhibiting truncated octahedral geometry (Figure 2). Each hexagonal face of the truncated octahedron is capped by a nbutylphosphonate. Synthesis and Structure of {S@Ag12S6@Ag36(tBuC C) 12( t BuS) 12 ( t BuPO 3 ) 8 }{S@Ag 16 ( t BuS) 8 (CH 3 OH) 2(H 2O) 4}· 5CH3OH (2). The synthetic procedure used to obtain {S@ Ag12S6@Ag36(tBuCC)12(tBuS)12(tBuPO3)8}{S@Ag16(tBuS)8(CH3OH)2(H2O)4}·5CH3OH (2) is similar to that of 1, except that nBuPO3H2 was replaced by tBuPO3H2. The structure of the anionic {S@Ag12S6@Ag36(tBuCC)12(tBuS)12(tBuPO3)8}6− cluster in 2 (Figure 3) is also similar to that found in 1, but

Figure 1. (a) Perspective view of the core−shell configuration of the nanocluster in complex 1. All hydrogen atoms and bonds between [Ag 36 ( t BuCC) 12 ( t BuS) 12 ( n BuPO 3 ) 2 ( n BuPO 3 H) 6 ] 2+ and [S@ Ag12S6]2− are omitted for clarity. The Ag···C bonds are indicated by broken lines. (b) Perspective view of the [S@Ag12S6]2− cluster core. The enclosed central sulfide ion is represented by a large light orangecolored sphere. Color code: Ag (shell), violet; Ag (core), sky blue; S (thiolate), yellow; S2−, light orange; P, green; O, red; C, gray. This color code for atoms applies to all figures unless otherwise modified.

In complex 1, a template sulfide ion is encapsulated within a Ag12S6 cluster composed of 12 silver(I) ions and six S2− anions, which is in turn covered by a cationic [Ag36(tBuC C)12(tBuS)12(nBuPO3)2(nBuPO3H)6]2+ cluster surface. The central S2− ion is generated from S−C bond cleavage of the t BuS− ligand, and the Ag12 unit can be regarded as a cuboctahedron composed of eight triangles and six squares. The S@Ag12 cuboctahedral geometry is analogous to I@Ag12 and I@Cu12 cores in [I@Ag12I4{S2P(CH2CH2Ph)2}6] and [PyH][I@Cu12(TpMo)4S16].10 Within the S@Ag12, the Ag−S distances fall in the range of 3.282−3.312 Å. The six squares faces of the cuboctahedron are each capped by a S2− ligand, and the eight trianglular faces are stabilized by two [nBuPO3]2− and six [nBuPO3H]− ligands. As a result, six S2− ions adopt the μ4bridging mode to link four Ag atoms from the Ag12 core with Ag−S bonds in the range of 2.680−2.822 Å. Three oxygen atoms in each phosphonate coordinate to three silver(I) ions of the Ag12 core, with Ag−Op (OP = oxygen atom of the phosphonate ligand) bond distance varying from 2.332 to 2.643 Å. The structure of the outer cationic [Ag36(tBuCC)12t ( BuS)12(nBuPO3)2(nBuPO3H)6]2+ cluster is composed of 12 t BuCC⊃Ag3 building blocks where an ethynide group is bound to a silver triangle in the μ3 coordination mode, as shown in Figures 2 and S1. Similar trinuclear silver motifs have been observed in many silver-ethynide clusters.4 The tBuC C⊃Ag3 units are linked together by 12 tert-butylthiolates as bridging ligands and eight n-butylphosphonates as structuredirecting templates. Thus, each tert-butylthiolate links three Ag3 triangles, while each Ag3 is coordinated by three tert-

Figure 3. (a) Perspective view showing the core−shell configuration of the anionic cluster {S@Ag 12 S 6 @Ag 36 ( t BuCC) 12 ( t BuS) 12 (tBuPO3)8}6− in 2. All peripheral tBu groups are omitted for clarity, and only tBu groups of tert-butylphosphonates are shown. (b) Perspective view of the cationic cluster {S@Ag16(tBuS)8}6+ in 2.

differs from it as all eight tert-butylphosphonate ligands are fully deprotonated. However, in contrast to 1, a silver(I)-thiolate cluster {S@Ag16(tBuS)8}6+ acts as a countercation. The structure of the cationic [S@Ag16(tBuS)8]6+ cluster is a wheel-shaped structure with outer diameter and thickness of ca. 8.75 and 3.84 Å, respectively (Figure 4). The central template S2− ion is encapsulated by the exterior Ag shell through the μ8 mode, with Ag−S bonds in the range of 2.945−3.055 Å. The eight tBuS− ligands adopt μ4 bridging mode to bind four silver atoms to form eight Ag4S square pyramids. Then the eight Ag4S square pyramids are arranged in corner-sharing mode to construct the Ag16S8 cluster. B

DOI: 10.1021/acs.inorgchem.7b01326 Inorg. Chem. XXXX, XXX, XXX−XXX

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butylthiolates to generate a silver(I) ethynide-thiolate cluster displaying hexagonal prismatic geometry (Figure 6). Each

Figure 4. (a) Space-filling model of the Ag16S8 shell cluster in 2. (b) Space-filling model of the Ag16S8 shell cluster viewed from its side. Color code: Ag (top and bottom layers of Ag4S4), violet; Ag (middle Ag8 ring), pink; S (thiolate), yellow. Figure 6. Left: Schematic representations of the assembly of {2tBuC C⊃Ag7} building units and tert-butylthiolates to produce the [Ag42(tBuCC)12(tBuS)18]12+ shell in 3 under the influence of nbutylphosphonate as structure-directing templates. Right: Two hexagonal faces each capped by a n-butylphosphonate. Topological representation of [Ag42(tBuCC)12(tBuS)18]12+ with {2tBuC C⊃Ag7} as connecting nodes, and {(tBuS)3} as linkers.

The Ag16S8 shell cluster can also be described as a layer structure according to the arrangement of three representative macrocycles parallel and arranged layer by layer: Ag4S4−Ag8− Ag4S4. As shown in Figure S2, the top and bottom Ag4S4 layers built of alternant Ag−S bonds, and the middle Ag8 ring is established by eight silver atoms giving the credit to the Ag···Ag interactions. Finally, the bilayer inversion Ag4S4 octagons connect with the interlayer Ag8 ring across the Ag−S bonds and Ag···Ag interactions to build the layer structure. Synthesis and Structure of {[(Ag3S3)S3]@Ag42(tBuC C)12(t BuS) 18(nBuPO 3)(nBuPO 3H)(NO3)4(CH3OH) 2(H 2O)2}· 4[H3O] (3). Complex 3 possesses a cationic [Ag42(tBuC C)12(tBuS)18(nBuPO3)(nBuPO3H)]9+ cluster shell consolidated by four nitrate anions, two CH3OH and two aqua ligands, which encapsulates a [Ag3S6]9− template cluster (Figure 5).

hexagonal face of the hexagonal prism is capped by a nbutylphosphonate, which adopts the μ6 bridging mode to coordinate to six silver atoms from six 2tBuCC⊃Ag7 aggregates, with Ag−Op bonds in the range of 2.423−2.762 Å. Each tBuS− ligand adopts the μ4 bridging mode to bind four silver atoms, with Ag−S bond distances ranging from 2.373 to 2.935 Å. The Ag42S18 shell can also be described as a layer structure according to the arrangement of five representative parallel macrocycles arranged layer by layer: Ag6S6−Ag12−Ag6S6− Ag12−Ag6S6. From Figure S4 we can see that the top and bottom Ag6S6 layers are built of alternate Ag−S bonds, and the two Ag12 layers are constructed with six Ag2 units. The middle Ag6S6 layer contains six S atoms from six thiolates and six Ag atoms from six 2tBuCC⊃Ag7 aggregate. As shown in Figure S5, the outer diameter of the nanoscale Ag42S18 cluster is 16.66 Å with a thickness 6.38 Å. The cationic clusters {Ag16(tBuS)8}8+, {Ag20(tBuS)10}10+,11 and [Ag42(tBuCC)12(tBuS)18(nBuPO3)(nBuPO3H)]9+ possess wheel-shaped structures. Their parallel top and bottom layers are composed of Ag4S4 octagons, Ag5S5 pentagons, and Ag6S6 dodecagons, respectively. Notably, a central phosphonate ligand links six silver atoms of Ag6S6 dodecagon. As compared to Ag16S8 and Ag20S10, more silver triangles, Ag2S triangles, and Ag4S square pyramids are present in 3. Thus, the outer diameter of 3 has more thickness than that of Ag16S8 and Ag20S10 clusters. Synthesis and Structure of {Ag3S3@Ag30(tBuCC)6t ( BuS)12(tBuPO3)(tBuPO3H)(hfac)6(H2O)2} (4). Our next attempt to employ tBuPO3H2 as a synthetic precursor, with {Ag(hfac)(THF)0.5} added to the reaction mixture, yielded {Ag3S3@Ag30(tBuCC)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6(H2O)2} (4). Complex 4 possesses a cationic [Ag30(tBuC C)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6]3+ cluster shell and a [Ag3S3]3− cluster core. The nearly planar [Ag3S3]3− cluster core is composed of a trianglular Ag3 unit held together by three S2− ions each binding two adjacent silver atoms. The Ag3 unit further attaches to an outer [Ag 30( tBuCC)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6]3+ shell through the three S2− ions. As a result, three S2− ions adopt the μ6 bridging mode to coordinate to six Ag atoms from the Ag3 core and Ag30 shell (Figure 7).

Figure 5. (a) Perspective view showing the core−shell configuration of the anionic cluster {[(Ag 3 S 3 )S 3 ]@Ag 42 ( t BuCC) 12 ( t BuS) 18 (nBuPO3)(nBuPO3H)} in 3. All hydrogen atoms, NO3−, H2O, CH3OH molecules, and bonds between [Ag42(tBuCC)12(tBuS)18(nBuPO3)(nBuPO3H)]9+ and [Ag3S6]9− are omitted for clarity. (b) View of the [Ag3S6]9− cluster core.

Notably, the central Ag3 core unit exhibits 2-fold orientational disorder with each set of Ag atoms having half occupancy. The Ag3 unit is further stabilized by linkage to an outer [Ag 42 ( t BuCC) 12 ( t BuS) 18 ( n BuPO 3 )( n BuPO 3 H)] 9+ shell through six S2− ions and two n-butylphosphonates. Of the six S2− ions, each adopts the μ7 bridging mode to coordinate to Ag atoms from the Ag3 core and Ag42 shell. The outer cationic [Ag42(tBuCC)12(tBuS)18(nBuPO3)n ( BuPO3H)]9+ cluster consists of six 2tBuCC⊃Ag7 aggregates that are linked together by 18 tert-butylthiolates as bridging ligands and two n-butylphosphonates as structuredirecting templates (Figure S3). The 2tBuCC⊃Ag7 aggregate comprises two Ag3 triangles linked by a bridging Ag atom. Adjacent Ag7 units are mutually connected by three tertC

DOI: 10.1021/acs.inorgchem.7b01326 Inorg. Chem. XXXX, XXX, XXX−XXX

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the μ4 bridging mode to bind four silver atoms, with Ag−S bond distances from 2.387 to 2.807 Å. The syntheses and structural characterization of 1−4 showed that large silver(I) sulfide-ethynide-thiolate clusters can be built up by an assembly process in solution. For 1−4, under suitable reaction conditions, each phosphonate ligand acts as a structure-directing template to induce the formation of a large silver ethynide-thiolate cluster shell. It is noteworthy that eight phosphonate ligands occur in constructing the same cluster shells, {Ag 3 6 ( t BuCC) 1 2 ( t BuS) 1 2 (BuPO 3 ) 2 (BuPO3H)6}, in 1 and 2. In contrast, the cluster shells of 3 and 4, {Ag42(tBuCC)12(tBuS)18(nBuPO3)(nBuPO3H)} and {Ag30(tBuCC)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6}, each contains only two phosphonate ligands. The present assembly reaction is also influenced by the choice of the silver salts: when AgNO3 and {Ag(hfac)(THF)0.5} were added in the synthetic procedure, complexes 3 and 4 were deposited instead of 1 and 2, respectively. The successive buildup of clusters 1−4 is associated with template clusters. The structures of Ag48 clusters in 1 features core−shell arrangements, Ag12S7@Ag36(tBuCC)12(tBuS)12(BuPO3)2(BuPO3H)6, in which the cuboctahedral silver sulfide cluster {Ag12S7} is encapsulated as a cluster template, whereas for 3 and 4, two silver ethynide-thiolate clusters, {Ag42(tBuC C)12(tBuS)18(nBuPO3)(nBuPO3H)} and {Ag30(tBuCC)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6}, encapsulate two planar silver sulfide clusters, {Ag3S6} and {Ag3S3}, respectively.

Figure 7. (a) Perspective view showing the core−shell configuration of the anionic cluster {[Ag3S3]@Ag30(tBuCC)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6} in 4. All hydrogen atoms, two aqua ligands and bonds between [Ag 30 ( t BuCC) 6 ( t BuS) 12 ( t BuPO3 )( t BuPO3 H)(hfac)6]3+ and [Ag3S3]3− are omitted for clarity. (b) View of the [Ag3S3]3− cluster core. Fluorine atoms are represented in light green color.

The structure of the outer cationic [Ag30(tBuCC)6(tBuS)12(tBuPO3)(tBuPO3H)(hfac)6]3+ cluster consists of three {[Ag10(tBuCC)2(tBuS)2(hfac)2]} units that are linked together by six tert-butylthiolates as bridging ligands and two tert-butylphosphonates as structure-directing templates (Figure S6). The ethynide group is capped by a butterfly-shaped Ag4 basket in the μ4 coordination mode, and two Ag4 baskets and two silver atoms are bridged by two tBuS− ligands to afford a {[Ag10(tBuCC)2(tBuS)2} unit. Two hfac ligands each coordinates to only one silver atom from a silver basket t BuCC⊃Ag4. Adjacent Ag10 units are mutually connected by two tertbutylthiolates to generate a silver(I) ethynide-thiolate cluster showing triangular prismatic geometry (Figure 8). Each triangular face of the triangular prism is capped by a tertbutylphosphonate. Each of two tert-butylphosphonates adopts the μ6 bridging mode to coordinate to six silver atoms from three {[Ag10(tBuCC)2(tBuS)2(hfac)2]}, with the Ag−Op bond in the range of 2.272−2.855 Å. Each tBuS− ligand adopts

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CONCLUSION

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EXPERIMENTAL SECTION

In summary, we have synthesized and structurally characterized four unprecedented high-nuclearity silver clusters based on silver sulfide clusters as cores and phosphonate-functionalized silver ethynide-thiolate clusters as their surface components. In compounds 1−4, the silver(I) aggregates tBuCC⊃Ag3, t BuCC⊃Ag4, and 2tBuCC⊃Ag7 are linked together by tert-butylthiolates as bridging ligands and phosphonates as structure-directing templates. For the first time, phosphonate as a structure-directing template is used to build up highnuclearity silver sulfide-ethynide-thiolate clusters. The present study paves the way to synthetic studies of novel silver ethynide-thiolate clusters employing potential precursors exemplified by phosphonic and arsonic acids.

All reagents employed are commercially available and were used as received without further purification. tBuSAg,12a tBuCCAg12b and {Ag(hfac)(THF)0.5}12c were prepared according to literature procedures. Elemental analyses for C, H, and N were performed with a PerkinElmer 2400 CHN elemental analyzer. The Fourier transform infrared (FT-IR) spectra were recorded from KBr pellets in the range 4000−400 cm−1 on a Bruker Equinox 55 spectrometer. The FT-IR spectra of compounds 1−4 are shown in Figures S7−S10 in Supporting Information. Caution! Due to the explosive nature of silver alkynyls, great care should be taken and only small amounts should be used. Synthesis of 1. tBuSAg (0.039 g, 0.20 mmol), tBuCCAg (0.023 g, 0.12 mmol), and AgBF4 (0.004 g, 0.02 mmol) were dissolved in 6 mL of methanol and dichloromethane under ultrasonication; then n BuPO3H2 (0.011 g, 0.08 mmol) was added under stirring to form a clear yellow solution. The resulting mixture was allowed to stand at room temperature for 24 h, and a yellow solution was collected by filtration. Slow evaporation of this solution afforded the product as yellow crystals. Yield: ca. 18% (based on nBuPO3H2). Elemental analysis (%) calcd for C152H294O24P8S19Ag48: C 21.37, H 3.44; found:

Figure 8. Left: Schematic representation of assembly of {[Ag10(tBuCC)2(tBuS)2(hfac)2]} building units and tert-butylthiolates to produce the [Ag30(tBuCC)6(tBuS)12(hfac)6]6+ shell in 4 under the influence of the tert-butylphosphonate as structure-directing templates. Right: Two triangular faces each capped by a tertbutylphosphonate. Topological representation of [Ag30(tBuCC)6(tBuS)12(hfac)6]6+ with {[Ag10(tBuCC)2(tBuS)2(hfac)2]} shown as connecting nodes, and {(tBuS)2} as linkers. D

DOI: 10.1021/acs.inorgchem.7b01326 Inorg. Chem. XXXX, XXX, XXX−XXX

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C 21.15, H 3.63. IR (KBr, cm−1): 3398 (O−H); 2023 (CC); 1057 (PO); 976 (P−O). Synthesis of 2. tBuSAg (0.059 g, 0.30 mmol), tBuCCAg (0.023 g, 0.12 mmol), and AgBF4 (0.008 g, 0.04 mmol) were dissolved in 6 mL of methanol and dichloromethane under ultrasonication; then t BuPO3H2 (0.011 g, 0.08 mmol) was added under stirring to form a clear yellow solution. The resulting mixture was allowed to stand at room temperature for 24 h, and a yellow solution was collected by filtration. Slow evaporation of this solution afforded the product as yellow crystals. Yield: ca. 15% (based on tBuPO3H2). Elemental analysis (%) calcd for C191H396O35P8S28Ag64: C 20.27, H 3.50; found: C 20.05, H 3.68. IR (KBr, cm−1): 3397 (O−H); 2054, 1384 (CC); 1049 (PO); 967 (P−O). Synthesis of 3. tBuSAg (0.049 g, 0.25 mmol), tBuCCAg (0.023 g, 0.12 mmol), AgBF4 (0.004 g, 0.02 mmol), and AgNO3 (0.002 g, 0.012 mmol) were dissolved in 6 mL of methanol and dichloromethane under ultrasonication; then nBuPO3H2 (0.003 g, 0.02 mmol) was added under stirring to form a clear yellow solution. The resulting mixture was allowed to stand at room temperature for 24 h, and a yellow solution was collected by filtration. Slow evaporation of this solution afforded the product as yellow crystals. Yield: ca. 11% (based on nBuPO3H2). Elemental analysis (%) calcd for C154H313O26N4P2S24Ag45: C 22.22, H 3.76 N 0.67; found: C 22.05, H 3.42, N 0.67. IR (KBr, cm−1): 3431(O−H); 2030 (CC); 1045 (PO); 964 (P−O). Synthesis of 4. tBuSAg (0.039 g, 0.20 mmol), tBuCCAg (0.023 g, 0.12 mmol), {Ag(hfac)(THF)0.5} (0.046 g, 0.12 mmol), and AgBF4 (0.004 g, 0.02 mmol) were dissolved in 6 mL of methanol and dichloromethane under ultrasonication; then tBuPO3H2 (0.003 g, 0.02 mmol) was added under stirring to form a clear yellow solution. The resulting mixture was allowed to stand at room temperature for 24 h, and a yellow solution was collected by filtration. Slow evaporation of this solution afforded the product as yellow crystals. Yield: ca. 13% (based on t BuPO 3 H 2 ). Elemental analysis (%) calcd for C122H191O20F36P2S15Ag33: C 21.64, H 2.82; found: C 21.78, H 2.65. IR (KBr, cm−1): 3431 (O−H); 2014 (CC); 1672 (CO); 1146 (C−F); 1049 (PO); 964 (P−O).

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ACKNOWLEDGMENTS We gratefully acknowledge financial support by National Natural Science Foundation of China (NO. 21201067, 51672093 and 51472095).

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REFERENCES

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b01326. Figures S1−S10 (PDF) Accession Codes

CCDC 1544875−1544878 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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Article

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (Y.-P.X.). *E-mail: [email protected] (X.L.). ORCID

Yun-Peng Xie: 0000-0002-4065-9809 Xing Lu: 0000-0003-2741-8733 Thomas C. W. Mak: 0000-0002-4316-2937 Notes

The authors declare no competing financial interest. E

DOI: 10.1021/acs.inorgchem.7b01326 Inorg. Chem. XXXX, XXX, XXX−XXX

Article

Inorganic Chemistry [Ag262S100(StBu)62(dppb)6]. Angew. Chem., Int. Ed. 2004, 43, 305; Angew. Chem. 2004, 116, 309. (b) Anson, C.; Eichhofer, A.; Issac, I.; Fenske, D.; Fuhr, O.; Sevillano, P.; Persau, C.; Stalke, D.; Zhang, J. Synthesis and Crystal Structures of the Ligand-Stabilized Silver Chalcogenide Clusters [Ag154Se77(dppxy)18], [Ag 3 2 0 (S t Bu) 6 0 S 1 3 0 (dppp) 1 2 ], [Ag 3 5 2 S 1 2 8 (S t C 5 H 1 1 ) 9 6 ], and [Ag490S188(StC5H11)114]. Angew. Chem., Int. Ed. 2008, 47, 1326; Angew. Chem. 2008, 120, 1346. (c) Zhou, K.; Qin, C.; Li, H.-B.; Yan, L.-K.; Wang, X.-L.; Shan, G.-G.; Su, Z.-M.; Xu, C.; Wang, X.-L. Assembly of a luminescent core-shell nanocluster featuring a Ag34S26 shell and a W6O216‑ polyoxoanion core. Chem. Commun. 2012, 48, 5844. (d) Li, G.; Lei, Z.; Wang, Q.-M. Luminescent Molecular Ag-S Nanocluster [Ag62S13(SBut)32](BF4)4. J. Am. Chem. Soc. 2010, 132, 17678. (e) Li, B.; Huang, R.-W.; Qin, J.-H.; Zang, S.-Q.; Gao, G.-G.; Hou, H.-W.; Mak, T. C. W. Thermochromic Luminescent Nest-Like Silver Thiolate Cluster. Chem. - Eur. J. 2014, 20, 12416. (f) Li, X.-Y.; Su, H.-F.; Yu, K.; Tan, Y.-Z.; Wang, X.-P.; Zhao, Y.-Q.; Sun, D.; Zheng, L.-S. A platonic solid templating Archimedean solid: an unprecedented nanometre-sized Ag37 cluster. Nanoscale 2015, 7, 8284. (g) Huang, R.W.; Xu, Q.-Q.; Lu, H.-L.; Guo, X.-K.; Zang, S.-Q.; Gao, G.-G.; Tang, M.-S.; Mak, T. C. W. Self-assembly of an unprecedented polyoxomolybdate anion [Mo20O66]12‑ in a giant peanut-like 62-core silver-thiolate nanocluster. Nanoscale 2015, 7, 7151. (h) Liu, H.; Song, C.-Y.; Huang, R. W.; Zhang, Y.; Xu, H.; Li, M.-J.; Zang, S.-Q.; Gao, G.G. Acid-Base-Triggered Structural Transformation of a Polyoxometalate Core Inside a Dodecahedrane-like Silver Thiolate Shell. Angew. Chem., Int. Ed. 2016, 55, 3699. (8) (a) Xie, Y.-P.; Mak, T. C. W. Silver (I)-ethynide clusters constructed with phosphonate-functionized polyoxovanadates. J. Am. Chem. Soc. 2011, 133, 3760. (b) Xie, Y.-P.; Mak, T. C. W. HighNuclearity Silver Ethynide Clusters Assembled with Phosphonate and Metavanadate Precursors. Angew. Chem., Int. Ed. 2012, 51, 8783. (c) Xie, Y.-P.; Mak, T. C. W. A pyrovanadate-templated silver (I)ethynide cluster circumscribed by macrocyclic polyoxovanadate (V). Chem. Commun. 2012, 48, 1123. (d) Xie, Y.-P.; Mak, T. C. W. Silver (I) ethynide coordination networks and clusters assembled with tertbutylphosphonic acid. Inorg. Chem. 2012, 51, 8640. (e) Xie, Y.-P.; Jin, J.-L.; Lu, X.; Mak, T. C. W. High-Nuclearity Silver Thiolate Clusters Constructed with Phosphonates. Angew. Chem., Int. Ed. 2015, 54, 15176; Angew. Chem. 2015, 127, 15391. (9) Crystallographic data: Complex 1: monoclinic, a = 29.887(5), b = 26.135(4), c = 21.633(6), β = 133.018(3), V = 12354(4) Å3, T = 173 K, space group C2m, Z = 2, λ = 0.71073 Å, ρ = 2.296 cm−3, μ(MoKα) = 3.959 mm−1, R1 = 0.1300, wR2 = 0.4011 for I > 2σ(I), GOF = 1.542. Complex 2: orthorhombic, a = 26.406(2), b = 29.654(2), c = 46.259(3), V = 36222(8) Å3, T = 173 K, space group Cmc21, Z = 4, λ = 0.71073 Å, ρ = 2.072 cm−3, μ(MoKα) = 3.604 mm−1, R1 = 0.0765, wR2 = 0.2271 for I > 2σ(I), GOF = 1.047. Complex 3: triclinic, a = 22.660(5), b = 23.927(5), c = 26.930(6), α = 84.804(5), β = 84.591(5), γ = 70.035(5), V = 13635(8) Å3, T = 173 K, space group P1̅, Z = 1, λ = 0.71073 Å, ρ = 2.027 cm−3, μ(MoKα) = 3.383 mm−1, R1 = 0.1465, wR2 = 0.3828 for I > 2σ(I), GOF = 1.055. Complex 4: monoclinic, a = 36.980(2), b = 21.615(1), c = 28.101(2), β = 122.760(2), V = 18888(6) Å3, T = 173 K, space group C2c, Z = 4, λ = 0.71073 Å, ρ = 2.379 cm−3, μ(MoKα) = 3.598 mm−1, R1 = 0.0735, wR2 = 0.1616 for I > 2σ(I), GOF = 1.157. CCDC 1544875 (1), 1544876 (2), 1544877 (3), and 1544878 (4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre. (10) (a) Wei, Z.-H.; Ni, C.-Y.; Li, H.-X.; Ren, Z.-G.; Sun, Z.-R.; Lang, J.-P. [PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)]: a unique tetracubane cluster derived from the S−S bond cleavage and the iodide template effects and its enhanced NLO performances. Chem. Commun. 2013, 49, 4836. (b) Liao, J.-H.; Latouche, C.; Li, B.; Kahlal, S.; Saillard, J.-Y.; Liu, C. W. A Twelve-Coordinated Iodide in a Cuboctahedral Silver(I) Skeleton. Inorg. Chem. 2014, 53, 2260. (11) (a) Sun, D.; Wang, H.; Lu, H.-F.; Feng, S.-Y.; Zhang, Z.-W.; Sun, G.-X.; Sun, D.-F. Two birds with one stone: anion templated ballshaped Ag56 and disc-like Ag20 clusters. Dalton Trans. 2013, 42, 6281.

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DOI: 10.1021/acs.inorgchem.7b01326 Inorg. Chem. XXXX, XXX, XXX−XXX