Citation: Yujie WANG, Laobang WANG, Zheng ZHANG, Qi LIU, Jianping LANG. Construction of W/Cu/S cluster-based supramolecular compounds via alkynyl/sulfur cycloaddition and their third-order nonlinear optical properties[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(10): 2069-2077. doi: 10.11862/CJIC.20250129 shu

Construction of W/Cu/S cluster-based supramolecular compounds via alkynyl/sulfur cycloaddition and their third-order nonlinear optical properties

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: 15 April 2025
Revised Date: 23 May 2025

Figures(4)

Using (Et₄N)[Tp*WS₃(CuCl)₃] (A) (Tp*=tris(3, 5-dimethylpyrazolyl)hydroborate) as a precursor cluster, a dechlorination reaction with Ag(OTf) was performed, followed by self-assembly with two bidentate pyridine ligands: 1, 3-bis[4-(pyridin-4-ylethynyl)phenyl]propane (L₁) and 1, 3-bis[4-(pyridin-4-ylethynyl)phenyl]propan-2-one (L₂). This led to the construction of two W/Cu/S cluster-based supramolecular rectangular macrocycles, [(Tp*WS₃Cu₂Cl)₄(L₁)₂]·6CH₂Cl₂ (1·6CH₂Cl₂) and [(Tp*WS₃Cu₂Cl)₄(L₂)₂]·6CH₂Cl₂ (2·6CH₂Cl₂). During their assembly process, one cycloaddition reaction between one alkynyl group of L₁ or L₂ and two S atoms of A occurred, which exerted an important impact on the formation of both supramolecular rectangular macrocycles. In addition, by introducing pyridine (Py) as a second ligand into the reaction systems of 1·6CH₂Cl₂ and 2·6CH₂Cl₂, a novel cluster [Tp*WS₃Cu₃(μ₃-Cl)(Py)₃](OTf) (3) was obtained. The three compounds were systematically characterized using single-crystal X-ray diffraction, electrospray ionization mass spectrometry, IR, and UV-Vis spectroscopy. Single crystal X-ray diffraction results confirmed that 1·6CH₂Cl₂ and 2·6CH₂Cl₂ have supramolecular rectangular macrocycle structures formed by two bidentate ligands (L₁ or L₂) bridging four [Tp*WS₃Cu₂Cl] cluster units. Cluster 3 has a cationic cubane-like structure with three pyridine molecules coordinating at three Cu(Ⅰ) centers of the [Tp*WS₃Cu₃(μ₃-Cl)]⁺ core. The Z-scan technique revealed that the solutions of 1·6CH₂Cl₂, 2·6CH₂Cl₂, and 3 showed good third-order nonlinear optical responses.
- W/Cu/S cluster,
- alkynyl/sulfur cycloaddition,
- supramolecular rectangular macrocycle,
- third-order nonlinear optical response
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