Citation: Yuxin LI, Mengqi ZHOU, Feifan LANG, Chunyan NI, Bing WU, Jianping LANG. Pyridine ligand-regulated structural diversity of W/Cu/S cluster-based supramolecules[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(7): 1429-1436. doi: 10.11862/CJIC.20260126 shu

Pyridine ligand-regulated structural diversity of W/Cu/S cluster-based supramolecules

Yuxin LI ¹ ,
Mengqi ZHOU ¹ ,
Feifan LANG ^1,, ,
Chunyan NI ¹ ,
Bing WU ^2,, ,
Jianping LANG ^1,,

1.
Suzhou Key Laboratory of Precision Transformation of Resource Molecules, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China
2.
Analysis and Testing Center, Soochow University, Suzhou, Jiangsu 215123, China

Corresponding author: Feifan LANG, fflangchem@suda.edu.cn Bing WU, wubing@suda.edu.cn Jianping LANG, jplang@suda.edu.cn
Received Date: 14 April 2026
Revised Date: 20 May 2026

Figures(4)

Reactions of (Et₄N)[Tp*WS₃] (A, Tp*=hydrotris(3, 5-dimethylpyrazolyl)borate) with [Cu(CH₃CN)₄]PF₆ and 3-pyridinecarboxaldehyde (L₁), 4-(2-aminoethyl)pyridine (L₂), and 3-(4-pyridyl)propanoic acid (L₃) in acetone (AC) or N, N-dimethylformamide (DMF), with the additional introduction of (Et₄N)I as a bridging iodide source when employing L₃, gave rise to three structurally distinct W/Cu/S cluster-based supramolecular compounds [Tp*WS₃Cu₃(L₁)₃(μ₃-AC)](PF₆)₂ (1), [Tp*WS₃Cu₂(L₂)(μ₂-DMF)]₂(PF₆)₂·2DMF (2·2DMF), and [Tp*WS₃Cu₃(μ₄-I)_0.5(L₃)₂]₂(PF₆)₃·2AC (3·2AC), respectively. All three clusters were structurally characterized by single-crystal X-ray diffraction and electrospray ionization mass spectrometry. The [Tp*WS₃Cu₃(L₁)₃(μ₃-AC)]²⁺ dication of 1 adopts a distorted cubane structure. The [Tp*WS₃Cu₂(L₂)(μ₂-DMF)]₂²⁺ dication of 2·2DMF consists of two corner-deficient cubane [Tp*WS₃Cu₂(μ₂-DMF)]⁺ units bridged by a pair of L₂ ligands to form a double corner-deficient cubane structure. The [Tp*WS₃Cu₃(μ₄-I)_0.5(L₃)₂]₂³⁺ trication of 3·2AC is composed of two corner-deficient cubane [Tp*WS₃Cu₃(L₃)₂]²⁺ units linked by μ₄-I^- bridges, giving a double-cubane architecture. The third-order nonlinear optical (NLO) properties of 1, 2·2DMF, and 3·2AC in solution were measured using the Z-scan technique, and they exhibited good third-order NLO responses.
- W/Cu/S clusters,
- supramolecules,
- ligand modulation,
- third-order nonlinear optical property
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