Structural Diversity of Copper(I) Cluster-Based Coordination Polymers with Pyrazine-2-thiol Ligand

Xiao-Qian Liang; Rakesh Kumar Gupta; Yun-Wu Li; Hui-Yan Ma; Lin-Na Gao; Chen-Ho Tung; Di Sun

doi:10.1021/acs.inorgchem.9b02919

Structural Diversity of Copper(I) Cluster-Based Coordination Polymers with Pyrazine-2-thiol Ligand

Inorg Chem. 2020 Mar 2;59(5):2680-2688. doi: 10.1021/acs.inorgchem.9b02919. Epub 2020 Feb 20.

Authors

Xiao-Qian Liang¹, Rakesh Kumar Gupta¹, Yun-Wu Li², Hui-Yan Ma², Lin-Na Gao³, Chen-Ho Tung¹, Di Sun^{1

2}

Affiliations

¹ 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.
² 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.
³ College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao, 266590, P. R. China.

PMID: 32077693
DOI: 10.1021/acs.inorgchem.9b02919

Abstract

Six novel copper(I) cluster-based coordination polymers (CPs) [Cu₉(pzt)₇Cl₂]_n (1), [Cu₂(pzt)Cl]_n (2), [Cu₄(pzt)₃Br]_n (3), [Cu(pzt)]_n (4), [Cu₄(pzt)₃I]_n (5), and [Cu₇(pzt)₆I]_n (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 {Cu_xS_y} 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 {Cu_xS_y} clusters-based CPs but also provides an interesting insight into structural modulation using crystal engineering concept.