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Structural Diversity of Copper(I) Cluster-Based Coordination Polymers with Pyrazine-2-thiol Ligand
Xiao-Qian Liang1, Rakesh Kumar Gupta1, Yun-Wu Li2
1Key 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.
Abstract:
Six novel copper(I) cluster-based coordination polymers (CPs) [Cu9(pzt)7Cl2] (1), [Cu2(pzt)Cl] (2), [Cu4(pzt)3Br] (3), [Cu(pzt)] (4), [Cu4(pzt)3I] (5), and [Cu7(pzt)6I] (6) 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 (4 and 6) or 3D (1-3, and 5) network based on diverse multinuclear {CuS} clusters. The structural evolutions of 1-6 are greatly influenced by types of metal halides and the ligand-to-metal molar ratio used in the reaction. Among them, compound 1 displays interesting temperature-dependent photoluminescence arising from triplet cluster-centered (3CC) excited state from the cluster metal core. Compounds 1-6 also exhibit photocurrent responses upon visible-light illumination (λ = 420 nm) in the order 6 > 5 > 3 > 1 > 4 > 2. 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.
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