Bromide‐Induced Formation of a Highly Symmetric Silver Thiolate Cluster Containing 36 Silver Atoms from an Infinite Polymeric Silver Thiolate

Liu, Xiaomin; Yang, Huayan; Zheng, Lan‐Sun

doi:10.1002/ejic.200900668

Cited by 15 publications

(8 citation statements)

References 19 publications

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“…Structures of SD/Ag90a and SD/Ag90b. With a combination of anion-template and geometrical-polyhedron strategies [31][32][33][34][35][36][37] and with careful choice of organic ligands ( t BuSH and PhPO 3 H 2 ) and anion templates (S 2− and PO 4 3− ), we one-pot synthesized Ag 90 nanoclusters under the solvothermal condition as dark brown or red rhombic crystals, depending on the polymorphs. They are stable under ambient conditions because the bulk sample of them can keep the color and morphology unchanged for at least one month.…”

Section: Resultsmentioning

confidence: 99%

A Keplerian Ag90 nest of Platonic and Archimedean polyhedra in different symmetry groups

Zhi

Schein

et al. 2020

Nat Commun

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Polyhedra are ubiquitous in chemistry, biology, mathematics and other disciplines. Coordination-driven self-assembly has created molecules mimicking Platonic, Archimedean and even Goldberg polyhedra, however, nesting multiple polyhedra in one cluster is challenging, not only for synthesis but also for determining the alignment of the polyhedra. Here, we synthesize a nested Ag 90 nanocluster under solvothermal condition. This pseudo-T h symmetric Ag 90 ball contains three concentric Ag polyhedra with apparently incompatible symmetry. Specifically, the inner (Ag 6) and middle (Ag 24) shells are octahedral (O h), an octahedron (a Platonic solid with six 3.3.3.3 vertices) and a truncated octahedron (an Archimedean solid with twenty-four 4.6.6 vertices), whereas the outer (Ag 60) shell is icosahedral (I h), a rhombicosidodecahedron (an Archimedean solid with sixty 3.4.5.4 vertices). The Ag 90 nanocluster solves the apparent incompatibility with the most symmetric arrangement of 2-and 3-fold rotational axes, similar to the arrangement in the model called Kepler's Kosmos, devised by the mathematician John Conway.

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Section: Resultsmentioning

confidence: 99%

A Keplerian Ag90 nest of Platonic and Archimedean polyhedra in different symmetry groups

Zhi

Schein

et al. 2020

Nat Commun

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“…The formation of M(I)−SR coordination polymers in solution from M(I) and HSR species is expected to afford an amplified signal for sensing . Considering the biological significance of cysteine, we report here a case study on the Ag(I)···Ag(I) interaction-facilitated Ag(I)−Cys coordination polymers for the spectral sensing of Cys. This study shows that the metallophilicity-facilitated M(I)−SR coordination polymers could indeed act as a spectral sensing ensemble for broad applications via modulating the metal−metal interaction in coordination polymers.…”

Section: Introductionmentioning

confidence: 99%

Metal−Metal-Interaction-Facilitated Coordination Polymer as a Sensing Ensemble: A Case Study for Cysteine Sensing

Shen

Zhang

et al. 2010

Langmuir

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A detailed investigation of the absorption and CD signals of Ag(I)-cysteine (Cys) aqueous solutions at buffered or varying pH has allowed us to suggest that coordination polymers are formed upon mixing Ag(I) and Cys bearing a Ag(I)-Cys repeat unit. The formation of the coordination polymers are shown to be facilitated by both the Ag(I)···Ag(I) interaction and the interaction between the side chains in the polymeric backbone. The former allows for an immediate spectral sensing of Cys with enantiomeric discrimination capacity with both high sensitivity and selectivity, and the contribution of the side-chain/side-chain interaction serves to guide extended sensing applications by means of modulating this interaction. With our preliminary data on the corresponding Cu(I)-Cys and Au(I)-Cys systems that exhibited similar spectral signals, we conclude that the M(I)-SR coordination polymers (M = Cu, Ag, or Au) could in general function as spectral sensing ensembles for extended applications. This sensing ensemble involves the formation of coordination polymers with practically no spectral background, thus affording high sensing sensitivity and selectivity.

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“…Although the twist feature was found in the Ag 9 trigonal prisms of compounds 1-4, the C 3 -symmetric geometry virtually endows them certain aesthetic significance, which may be causedb yt he synergetic effect of the high steric-hindrance capping thiolate ligand, the long diphosphine bridge, and the presence of a3 -fold axis in each of the anion used. The general formation of these twisted Ag 9 trigonal prisms is interesting andi nspires us to perform several comparable experiments (Scheme 2b)t ou nderstand the underlying principle of the synergetic effect of the high steric-hindrance capping thiolate ligand and the long diphosphine bridge.F irstly, when the long dpph ligand was replaced by the shorter dpppe (1,5-bis(diphenylphosphino)pentane) ligand and the bulkierd ppf (1,1'-bis(diphenylphosphino)ferrocene) ligand in similara ssembly systems, we found another three silversulfur clusters,t hat is, (HNEt 3 ) 2 [Ag 10 S 2 (tBuC 6 H 4 S) 6 (dpppe) 6 (7). In contrast, when as maller thiolate ligand was used, [Ag 7 (iBuS) 3 (dppf) 3 (NO 3 )(H 2 O)]·3NO 3 (8)w as isolated.…”

Section: X-ray Structures and Assembly Discussionmentioning

confidence: 91%

“…[4] In the highest nuclearity silver-sulfur clusters [5] such as Ag 320 , Ag 352 ,a nd Ag 490 ,n oo bvious structural aesthetics can be found in them, where the arrangemento fs ilver and sulfur atoms is chaotic. Several medium-nuclearity silver-sulfur clusters, such as the C 3i -symmetric tabular [Br@Ag 36 (tBuC 6 H 4 S) 36 ] À [6] and the spherical [(S 2À )@Ag 56 S 12 (StBu) 20 ], [7] the pseudo C 5i -symmetric [(CO 3 2À )@Ag 20 (StBu) 10 (OAc) 8 (dmf) 4 ], [7] the pseudo C 3 -symmetric [Ag 21 {S 2 P(OiPr) 2 } 12 ] + [8a] and [Ag 11 (H)(S 2 CNPr 2 ) 9 ] + , [8b] the T h -symmetric [Ag 8 (X){S 2 P(OEt) 2 } 6 ] + (X = Fa nd Cl), [8c] the pseudo C 5symmetric [Ag 50 S 7 (tBuC 6 H 4 S) 40 ] 4À , [9] the S 6 -symmetric [ H 4 Ag 8 (2mpa) 6 (PPh 3 ) 6 ]( 2-Hmpa = 2-mercaptopropionic acid), [10] show beautiful molecular symmetry that could be represented by Schçenflies symbols. However,s uccessful assemblyo ft hese clusters is often as poradic case.…”

Section: Introductionmentioning

confidence: 99%

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

Zhou

et al. 2016

Chemistry A European J

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A general class of C3 -symmetric Ag9 clusters, [Ag9 S(tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )] (1), [Ag9 (tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )2 ]⋅CF3 SO3 (2), [Ag9 (tBuC6 H4 S)6 (dpph)3 (NO3 )2 ] ⋅NO3 (3), and [Ag9 (tBuC6 H4 S)7 (dpph)3 (Mo2 O7 )0.5 ]2 ⋅2 CF3 COO (4) (dpph=1,6-bis(diphenylphosphino)hexane), with a twisted trigonal-prism geometry was isolated by the reaction of polymeric {(HNEt3 )2 [Ag10 (tBuC6 H4 S)12 ]}n , 1,6-bis(diphenylphosphino)hexane, and various silver salts under solvothermal conditions. The structures consist of discrete clusters constructed from a girdling Ag9 twisted trigonal prism with the top and bottom trigonal faces capped by diverse anions (i.e., S(2-) and CF3 SO3 (-) for compound 1, 2×CF3 SO3 (-) for compound 2, 2×NO3 (-) for compound 3, and tBuC6 H4 S(-) and Mo2 O7 (2-) for compound 4). This trigonal prism is bisected by another shrunken Ag3 trigon at its waist position. Interestingly, two inversion-related Ag9 trigonal-prismatic clusters are dimerized by the Mo2 O7 (2-) ion in compound 4. The twist is amplified by the bulkier thiolate, which also introduces high steric-hindrance for the capping ligand, that is, the longer dpph ligand. Four more silver-sulfur clusters (namely, compounds 5-8) with their nuclearity ranging from 6-10 were solely characterized by single-crystal X-ray diffraction to verify the above-described synergetic effect of mixed ligands in the construction of Ag9 twisted trigonal prisms. Surprisingly, only cluster 1 emits yellow luminescence at λ=584 nm at room temperature, which may be attributed to a charge transfer from the S 3p orbital to the Ag 5s orbital, or mixed with metal-centered (MC) d(10) →d(9) s(1) transitions. Upon cooling from 300 to 80 K, the emission intensity was enhanced along with a hypsochromic shift. The good linear relationship between the maximum emission intensity and the temperature for compound 1 in the range of 180-300 K indicates that this is a promising molecular luminescent thermometer. Furthermore, cyclic voltammetric studies indicated that the diffusion- and surface-controlled redox processes were determined for compounds 1 and 3 as well as compound 4, respectively.

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Bromide‐Induced Formation of a Highly Symmetric Silver Thiolate Cluster Containing 36 Silver Atoms from an Infinite Polymeric Silver Thiolate

Abstract: Owing to its good affinity with Ag + , Br -is able to truncate a silver thiolate polymer and induce the formation of a highnuclearity silver thiolate nanocluster, [Br@Ag 36 (SC 6 H 4 tBu-

Cited by 15 publications

References 19 publications

A Keplerian Ag90 nest of Platonic and Archimedean polyhedra in different symmetry groups

A Keplerian Ag90 nest of Platonic and Archimedean polyhedra in different symmetry groups

Metal−Metal-Interaction-Facilitated Coordination Polymer as a Sensing Ensemble: A Case Study for Cysteine Sensing

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

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