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Synthesis, Crystal Structures, and Photoluminescent Properties of the Cu(I)/X/α,ω-Bis(benzotriazole)alkane Hybrid Family (X = Cl, Br, I, and CN)

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posted on 16.02.2009, 00:00 by Man-Cheng Hu, Yan Wang, Quan-Guo Zhai, Shu-Ni Li, Yu-Cheng Jiang, Yong Zhang
This work focused on a systematic investigation of the influences of the spacer length of the flexible α,ω-bis(benzotriazole)alkane ligands and counteranions on the overall molecular architectures of hybrid structures that include Cu(I). Using the self-assembly of CuX (X = Cl, Br, I, or CN) with the five structurally related flexible organic ligands (L1L5) under hydro(solvo)thermal conditions, we have synthesized and characterized 10 structurally unique materials of the Cu(I)/X/α,ω-bis(benzotriazole)alkane organic−inorganic hybrid family, {[CuCl]2(L1)}n (1), {[CuBr](L2)}n (2), {[CuCl]2(L3)}n (3), {[CuI]2(L4)}n (4), {[CuBr]2(L4)}n (5), {[CuBr]3(L5)}n (6), {[CuCN]2(L1)}n (7), {[CuCl]4(L2)}n (8), {[CuBr]4(L2)}n (9), and {[CuCl]2(L4)}n (10), by means of elemental analyses, X-ray powder diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, and photoluminescence measurements. Single-crystal X-ray analyses showed that the inorganic subunits in these compounds were {Cu2X2} binuclear clusters (1 and 2), {Cu4X4} cubane clusters (4, 5, and 10), {CuX}n single chains (3 and 7), a {Cu3X3}n ladderlike chain (6), and unprecedented {Cu8X8}n ribbons (8 and 9). The increasing dimensionality from 1-D (14) to 2-D (5 and 6) to 3-D (710) indicates that the spacer length and isomerism of the bis(benzotriazole)alkane ligands play an essential role in the formation of the framework of the Cu(I) hybrid materials. The influence of counteranions and π−π stacking interactions on the formation and dimensionality of these hybrid coordination polymers has also been explored. In addition, all the complexes exhibit high thermal stability and strong fluorescence properties in the solid state at ambient temperature.