| W/Cu/S簇基超分子大环及其三阶非线性光学性质 |
| W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses |
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| 摘要: 以前驱簇[Et4N][Tp*WS3(CuCl)3]与三氟甲烷磺酸银(AgOTf)及3个有机桥联配体2，5-二(吡啶-4-基)噻吩(L1)、5，5'-双(4-吡啶基)-2,2'-双噻吩(L2)和2，7-双(4-吡啶基)芘(L3)分别反应，得到了3个阳离子型W/Cu/S簇基超分子大环化合物[(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)和[(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)(L3)]2(OTf)2·2DMF (3·2DMF)，其中Tp*=hydridotris (3，5-dimethylpyrazol-1-yl) borate。对3个化合物分别进行了单晶X射线衍射、核磁、质谱、红外光谱、紫外可见光谱和元素分析等结构表征。单晶X射线衍射结果表明，3个大环的主体均是由2个L1、L2和L3配体和3个氯桥连接的[(Tp*WS3Cu3)2(μ-Cl)2(μ4-Cl)]2+阳离子簇核组成。3个大环通过不同方式堆叠形成三维结构。核磁氢谱(1H NMR)和电喷雾飞行质谱(ESI-TOF MS)结果表明这些化合物在溶液中有较好的稳定性。Z扫描测试结果表明，3个化合物的溶液有一定的三阶非线性光学响应。 |
| 关键词: W/Cu/S簇 组装 超分子大环 结构 三阶非线性光学响应 |
| 基金项目: 国家自然科学基金(No.22301204，21773163)和苏州市资源分子精准转化重点实验室(No.SZS201905)资助。 |
| Abstract: 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]. |
| Keywords: W/Cu/S clusters assembly supramolecular macrocycles structures third-order nonlinear optical responses |
| 投稿时间：2024-05-16 修订日期：2024-07-12 |
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| 黄志文,刘琦,郎建平.W/Cu/S簇基超分子大环及其三阶非线性光学性质[J].无机化学学报,2025,41(1):79-87. |
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| Support information: 相关附件： 20240184_Revised_Supporting_Information.doc |
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