A classical [V10O28]6− anion templated high-nuclearity silver thiolate cluster

Li, Li; Zhu, Yan Jie; Han, Bao-Liang; Wang, Qiong Yi; Zheng, Lu-Ming; Feng, Lei; Sun, Di; Wang, Zhi

doi:10.1039/d2cc03003a

Cited by 8 publications

(5 citation statements)

References 38 publications

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“…In addition, mass spectrometry of 1 – 3 was not successful because they decomposed immediately when dissolved in solution (Figures S10–S13). Most of the NCs reported in the literature have an even number of valence electrons, implying that the NCs with an odd number of valence electrons cannot be isolated easily. We performed ESR spectroscopy on 2 and 3 to confirm that they have a closed-shell electronic structure (Figures S14–S16).…”

Section: Resultsmentioning

confidence: 99%

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation

Horita,

Hossain,

Ishimi

et al. 2023

J. Am. Chem. Soc.

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Electronic structures of anion-templated silver nanoclusters (Ag NCs) are not well understood compared to conventional, template-free Ag NCs. In this study, we synthesized three new aniontemplated Ag NCs, namely [S@Ag 17 (S-4CBM) 15 (PPh 3 ) 5 ] 0 , [S@Ag 18 (S-4CBM) 16 (PPh 3 ) 8 ] 0 , and [Cl@Ag 18 (S-4CBM) 16 (PPh 3 ) 8 ][PPh 4 ], where S-4CBM = 4-chlorobenzene methanethiolate, and single-crystal X-ray crystallography revealed that they have S@Ag 6 , S@Ag 10 , and Cl@Ag 10 cores, respectively. Investigation of their electronic structures by optical spectroscopy and theoretical calculations elucidated the following unique features: (1) their electronic structures are different from those of template-free Ag NCs described by the superatomic concept;(2) optical absorption in the range of 550−400 nm for S 2− -templated Ag NCs is attributed to the charge transitions from S 2− -templated Ag-cage orbitals to the s-shaped orbital in the S 2− moiety; (3) the Cl − -templated Ag NCs can be viewed as [Cl@Ag 18 (S-4CBM) 16 (PPh 3 ) 8 ] 0 [PPh 4 ] 0 rather than the ion pair [Cl@Ag 18 (S-4CBM) 16 (PPh 3 ) 8 ] − [PPh 4 ] + ; and (4) singlet-coupled singly occupied orbitals are involved in the optical absorption of the Cl −templated Ag NC.

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Section: Resultsmentioning

confidence: 99%

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation

Horita,

Hossain,

Ishimi

et al. 2023

J. Am. Chem. Soc.

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“…The synthesis of structurally well-defined Ag(0)-containing nanoclusters has been performed for over a decade, but the instability of silver nanoclusters restricts their structural modulation. [35][36][37][38][39] Currently, several effective methods have been developed to fine-tune the nanocluster structures, including heterometal doping, [40][41][42] ligand engineering, [43][44][45][46][47][48] counter ion template, [49][50][51][52] and so on. The ligand engineering strategy is considered one of the most effective ways to regulate the structure and supramolecular assembly of nanoclusters.…”

Section: Introductionmentioning

confidence: 99%

“…Currently, several effective methods have been developed to fine-tune the nanocluster structures, including heterometal doping, 40–42 ligand engineering, 43–48 counter ion template, 49–52 and so on. The ligand engineering strategy is considered one of the most effective ways to regulate the structure and supramolecular assembly of nanoclusters.…”

Section: Introductionmentioning

confidence: 99%

Construction of novel Ag(0)-containing silver nanoclusters by regulating auxiliary phosphine ligands

Ma,

Zhai,

Huang

et al. 2024

Nanoscale

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“…2À , [39,40] CO 3 2À , [41][42][43][44][45][46][47][48][49][50] NO 3 À , [51] MoO 4 2À , [35] [Mn III Mn IV 2 Mo 14 O 56 ] 17À , [52] Mo 6 O 22 8À , [53] [Mo 20 O 66 ] 12À , [54] [EuW 10 O 36 ] 9À , [55] VO 4 3À , [56] AsO 4 3À , [57] SO 4 2À , [58,59] P 5 W 30 , [60] [V 10 O 28 ] 6À [61] ), and organic anions (C 4 O 4 2À , [62] C 2 O 4 2À [63] ), etc. Among them, the carbonate ion (CO 3 2À ) is a perfect anion template.…”

Section: Introductionmentioning

confidence: 99%

Carboxylate Ligand‐supported Ag_n (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

Liu

Zhou

et al. 2023

Chemistry An Asian Journal

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Structural transformation is important for the study of silver cluster compounds, in which controlled synthesis of their shapes and sizes via anion template-driven is one key scientific question. In this work, the CO 3 2À anion templates were captured by the [ t BuC�CAg] n system under the stimulation induced by carboxylate ligand CF 3 COO À /PhCOO À , and two silver alkynyl clusters [(CO 3 2À )@Ag 21 ( t BuC�C) 16 (CF 3 COO) 3 (H 2 O)]•DMF•2CH 2 Cl 2 (1) and [(CO 3 2À ) 2 @Ag 24 ( t BuC�C) 16 (PhCOO) 4 ]•CH 3 OH•4DMF (2) have been successfully isolated and charactered. With the increase of the number of CO 3 2Àtemplates from single to double, the outer silver atoms from twenty-one to twenty-four, accompanied by the growth of the cluster skeleton from 9.8 Å × 6.9 Å of the (CO 3 2À )@Ag 21 unit to 10.5 Å × 7.3 Å of the (CO 3 2À ) 2 @Ag 24 unit. In addition, the syntheses, structures, photocurrent responses, cyclic voltammetry characteristics, luminescence, and photodegradation of compounds 1 and 2 have been studied.

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A classical [V₁₀O₂₈]⁶⁻ anion templated high-nuclearity silver thiolate cluster

Abstract: Polyoxovanadates (POVs) as templates are still scarcely observed in silver clusters. Herein, the largest known POV-based silver cluster (Ag50) was synthesized, which is a core-shell conformation composed of the in-situ...

Cited by 8 publications

References 38 publications

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation

Construction of novel Ag(0)-containing silver nanoclusters by regulating auxiliary phosphine ligands

Carboxylate Ligand‐supported Ag_n (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

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A classical [V10O28]6− anion templated high-nuclearity silver thiolate cluster

Abstract: Polyoxovanadates (POVs) as templates are still scarcely observed in silver clusters. Herein, the largest known POV-based silver cluster (Ag50) was synthesized, which is a core-shell conformation composed of the in-situ...

Cited by 8 publications

References 38 publications

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation

Construction of novel Ag(0)-containing silver nanoclusters by regulating auxiliary phosphine ligands

Carboxylate Ligand‐supported Agn (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

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A classical [V₁₀O₂₈]⁶⁻ anion templated high-nuclearity silver thiolate cluster

Carboxylate Ligand‐supported Ag_n (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions