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{mu-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 Cu-2(mu(2)-I)(2) clusters as secondary building units (SBUs). Notably, layer A, interconnected by bridging L1 ligands, contains exclusively dinuclear units with short Cu center dot center dot center dot Cu separations [2.6485(7) angstrom; 115 K]. In contrast, layer B exhibits Cu''''''Cu distances of 2.8133(8) angstrom. The same network is observed when CuBr reacts with Ll. In the 2D network of [Cu2Br2{mu-E-PhS(CH2CH=CHCH2)SPh}(2)](n) (1b), isotype to 1a, one square -grid -type layer contains Cu-2(mu(2)-Br)(2) SBUs with short Cu center dot center dot center dot Cu contacts [2.7422(6) angstrom at 115K], whereas the next layer incorporates exclusively Cu2(p2-Br)2 SBUs with a significantly longer Cu Cu separation [2.9008(10) angstrom] The evolution of the crystallographic parameters of la and lb was monitored between 115 and 275 K. Conversely, the isomeric Z-PhS(CH2CH=CHCH2)SPh ligand L2 reacts with Cul to form the 2D CP [Cu-4(mu(3)-I)(4)(mu-Z-PhS(CH2CH=CHCH2)SPh}(2)](n) (2a) with closed-cubane SBUs. A dinuclear zero -dimensional complex [Cu2Br2{mu-Z-PhS(CH2CH=CHCH2)Sa}(2)] (2b) is formed when CuBr is reacted with L2. Upon reaction of E-TolS(CH2CH=CHCH2)STol, L3, with CuI, the 2l5 CP [{Cu(mu(3)-I)}(2)(mu-L3)](n) containing parallel -arranged infinite inorganic staircase ribbons, is generated. When CuX reacts with Z-TolS(CH2CH=CHCH2)STol, L4, the isostructural 2D CPs [Cu2X2{mu-TolS(CH2CH=CHCH2)STol}(2)] (4a X = I; 4b X = Br) are formed. In contrast to the CPs la,b, the layers based on rhombic grids of 4a,b incorporate Cu-2(mu(2)-X)(2) SBUs featuring uniformly identical Cu center dot center dot center dot Cu distances within each layer. The TGA traces showed that all these materials are stable up to similar to 200 inverted perpendicular C. Moreover, the photophysical properties have been studied, including absorption, emission, excitation spectra, and emission lifetimes at 298 and 77 K. The spectra were interpreted using density functional theory (DFT) and time -dependent DFT calculations.