1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu2X2)n (X = I, Br; n = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties

CuI reacts with E-PhS(CH2CH═CHCH2)SPh, L1, to afford the coordination polymer (CP) [Cu2I2{μ-E-PhS(CH2CH═CHCH2)SPh}2]n (1a). The unprecedented square-grid network of 1 is built upon alternating two-dimensional (2D) layers with an ABAB sequence and contains rhomboid Cu2(μ2-I)2 clusters as secondary building units (SBUs). Notably, layer A, interconnected by bridging L1 ligands, contains exclusively dinuclear units with short Cu···Cu separations [2.6485(7) A; 115 K]. In contrast, layer B exhibits Cu···Cu distances of 2.8133(8) A. The same network is observed when CuBr reacts with L1. In the 2D network of [Cu2Br2{μ-E-PhS(CH2CH═CHCH2)SPh}2]n (1b), isotype to 1a, one square-grid-type layer contains Cu2(μ2-Br)2 SBUs with short Cu···Cu contacts [2.7422(6) A at 115K], whereas the next layer incorporates exclusively Cu2(μ2-Br)2 SBUs with a significantly longer Cu···Cu separation [2.9008(10) A]. The evolution of the crystallographic parameters of 1a and 1b was monitored between 115 and 275 K. Conversely, the isomeric...