Citation: Zhiwen HUANG, Qi LIU, Jianping LANG. W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184 shu

W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses

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: 16 May 2024
Revised Date: 12 July 2024

Figures(5)

The precursor cluster [Et₄N][Tp*WS₃(CuCl)₃] was treated with silver trifluoromethane sulfonate (AgOTf), followed by the assembly with three bridging ligands 2, 5-di(pyridin-4-yl)thiophene (L₁), 5, 5'-bis(4-pyridinyl)-2, 2'-bi- thiophene (L₂), and 2, 7-di(4-pyridinyl)pyrene (L₃), resulting in three cationic W/Cu/S cluster-based supramolecular macrocycles [(Tp*WS₃Cu₃)₂(μ-Cl)₂(μ₄-Cl)(L₁)]₂(OTf)₂(1), [(Tp*WS₃Cu₃)₂(μ-Cl)₂(μ₄-Cl)(L₂)]₂(OTf)₂·2CHCl₃(2·2CHCl₃), and [(Tp*WS₃Cu₃)₂(μ-Cl)₂(μ₄-Cl)(L₃)]₂(OTf)₂·2DMF (3·2DMF), respectively. Structural characterizations including single-crystal X-ray diffraction, NMR spectroscopy, mass spectrometry, IR spectroscopy, UV-Vis spectroscopy, and elemental analysis were carried out for these compounds. X-ray analysis revealed that the main backbones of the three macrocycles are composed of a pair of L₁, L₂, or L₃ ligands and three chlorine-bridged [(Tp*WS₃Cu₃)₂(μ-Cl)₂(μ₄-Cl)]²⁺ cationic cluster cores. And they form 3D structures by stacking in different ways. The ¹H NMR and electrospray ionization time- of-flight mass spectrometry (ESI-TOF MS) results indicated their good stability in solution. These three compounds exhibited enhanced third-order nonlinear optical properties in DMF compared to the precursor [Et₄N][Tp*WS₃(CuCl)₃].
- W/Cu/S clusters,
- assembly,
- supramolecular macrocycles,
- structures,
- third-order nonlinear optical responses
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