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

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.