Citation: Xiaohang JIN, Qi LIU, Jianping LANG. Room‑temperature solid‑state synthesis, structure, and third‑order nonlinear optical properties of phosphine‑ligand‑protected silver thiolate clusters[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(8): 1505-1512. doi: 10.11862/CJIC.20250125 shu

Room‑temperature solid‑state synthesis, structure, and third‑order nonlinear optical properties of phosphine‑ligand‑protected silver thiolate clusters

Suzhou Key Laboratory of Precision Transformation of Resource Molecules, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China

Corresponding author: Qi LIU, qi.liu@suda.edu.cn Jianping LANG, jplang@suda.edu.cn
Received Date: 13 April 2025
Revised Date: 2 May 2025

Figures(5)

The cluster precursor [Ag₉(Tab) ₈(MeCN)₈]₂(PF₆)₁₈·4MeCN (Ag₁₈, Tab=4-(trimethylammonio)benzenethio- late), MeCN=acetonitrile) was subjected to solid-state grinding reactions with two phosphine ligands, triphenylphos- phine (L₁) and diphenyl- 2-pyridylphosphine (L₂), respectively. The obtained solid powders were dissolved in DMF/ EtOH solvents, followed by centrifugal separation. Two silver thiolate clusters protected by phosphine ligands were obtained from the supernatant through Et₂O diffusion crystallization: [Ag₇(Tab)₆(L₁)₆Cl] (PF₆)₆·8DMF (1) and [Ag₁₇(Tab)₂₀(L₂) ₂](PF ₆)₁₇·32DMF (2). Both compounds were thoroughly characterized via single-crystal X-ray diffrac- tion, powder X -ray diffraction, infrared spectroscopy, ultraviolet- visible spectroscopy, thermogravimetric, and ele- mental analysis. Single-crystal X-ray diffraction analysis revealed that both clusters are stabilized by a combination of phosphine and Tab ligands, with the diphenyl-2-pyridylphosphine ligand in 2 exhibiting simultaneous coordina- tion through both phosphorus and nitrogen atoms. Z-scan measurements demonstrated that both compounds in solu- tion exhibit notable third-order nonlinear optical responses.
- silver-thiolate clusters,
- room-temperature solid-state synthesis,
- phosphine ligands,
- third-order nonlinear optical responses
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