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 S

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• 作者：Antoine Bonnot ; Michael Knorr ; Fabrice Guyon ; Marek M. Kubicki ; Yoann Rousselin ; Carsten Strohmann ; Daniel Fortin ; Pierre D. Harvey
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：February 3, 2016
• 年：2016
• 卷：16
• 期：2
• 页码：774-788
• 全文大小：736K
• ISSN：1528-7505

文摘

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) ?; 115 K]. In contrast, layer B exhibits Cu···Cu distances of 2.8133(8) ?. 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) ? at 115K], whereas the next layer incorporates exclusively Cu₂(μ₂-Br)₂ SBUs with a significantly longer Cu···Cu separation [2.9008(10) ?]. The evolution of the crystallographic parameters of 1a and 1b was monitored between 115 and 275 K. Conversely, the isomeric Z-PhS(CH₂CH═CHCH₂)SPh ligand L2 reacts with CuI to form the 2D CP [Cu₄(μ₃-I)₄(μ-Z-PhS(CH₂CH═CHCH₂)SPh}₂]_n (2a) with closed-cubane SBUs. A dinuclear zero-dimensional complex [Cu₂Br₂{μ-Z-PhS(CH₂CH═CHCH₂)SPh}₂] (2b) is formed when CuBr is reacted with L2. Upon reaction of E-TolS(CH₂CH═CHCH₂)STol, L3, with CuI, the 2D CP [{Cu(μ₃-I)}₂(μ-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{μ-Z-TolS(CH₂CH═CHCH₂)STol}₂] (4a X = I; 4b X = Br) are formed. In contrast to the CPs 1a,b, the layers based on rhombic grids of 4a,b incorporate Cu₂(μ₂-X)₂ SBUs featuring uniformly identical Cu···Cu distances within each layer. The TGA traces showed that all these materials are stable up to ～200 °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.