Liang Xiao-Qian, Gupta Rakesh Kumar, Li Yun-Wu, Ma Hui-Yan, Gao Lin-Na, Tung Chen-Ho, Sun Di
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, and State Key Laboratory of Crystal Materials Shandong University, Jinan, 250100, P. R. China.
Shandong Provincial Key Laboratory/Collaborative Innovation Center of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, P. R. China.
Inorg Chem. 2020 Mar 2;59(5):2680-2688. doi: 10.1021/acs.inorgchem.9b02919. Epub 2020 Feb 20.
Six novel copper(I) cluster-based coordination polymers (CPs) [Cu(pzt)Cl] (), [Cu(pzt)Cl] (), [Cu(pzt)Br] (), [Cu(pzt)] (), [Cu(pzt)I] (), and [Cu(pzt)I] () were solvothermally synthesized using Hpzt (Hpzt = pyrazine-2-thiol) ligand and well-characterized by elemental analysis, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction (SCXRD). Six CPs exhibit either 2D ( and ) or 3D (-, and ) network based on diverse multinuclear {CuS} clusters. The structural evolutions of - are greatly influenced by types of metal halides and the ligand-to-metal molar ratio used in the reaction. Among them, compound displays interesting temperature-dependent photoluminescence arising from triplet cluster-centered (CC) excited state from the cluster metal core. Compounds - also exhibit photocurrent responses upon visible-light illumination (λ = 420 nm) in the order > > > > > . This work not only shows the structural diversity of {CuS} clusters-based CPs but also provides an interesting insight into structural modulation using crystal engineering concept.
六种新型基于铜（I）簇的配位聚合物（CPs）[Cu(pzt)Cl]（）、[Cu(pzt)Cl]（）、[Cu(pzt)Br]（）、[Cu(pzt)]（）、[Cu(pzt)I]（）和[Cu(pzt)I]（）通过使用Hpzt（Hpzt = 吡嗪 - 2 - 硫醇）配体溶剂热合成，并通过元素分析、红外（IR）光谱、粉末X射线衍射（PXRD）和单晶X射线衍射（SCXRD）进行了充分表征。六种CPs基于不同的多核{CuS}簇展现出二维（和）或三维（ - 、和）网络结构。 - 的结构演变受到反应中使用的金属卤化物类型和配体与金属摩尔比的极大影响。其中，化合物 表现出有趣的温度依赖性光致发光，源于簇金属核的三重态簇中心（CC）激发态。化合物 - 在可见光照射（λ = 420 nm）下也表现出光电流响应，顺序为 > > > > > 。这项工作不仅展示了基于{CuS}簇的CPs的结构多样性，还利用晶体工程概念为结构调控提供了有趣的见解。
