Synthesis, crystal structures, and photoluminescent properties of the Cu(I)/X/alpha,omega-bis(benzotriazole)alkane hybrid family (X = Cl, Br, I, and CN).
Synthesis, crystal structures, and photoluminescent properties of the Cu(I)/X/alpha,omega-bis(benzotriazole)alkane hybrid family (X = Cl, Br, I, and CN).
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DOI：
10.1021/ic801574k
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发表时间：
2009-01
影响因子：
4.6
通讯作者：
Mancheng Hu;Yan Wang;Q. Zhai;Shu’ni Li;Yucheng Jiang;Yong Zhang
中科院分区：
文献类型：
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作者：
Mancheng Hu;Yan Wang;Q. Zhai;Shu’ni Li;Yucheng Jiang;Yong Zhang
本研究的重点是系统地研究柔性α - - - -二（苯并三唑）烷配体和反阴离子的间隔长度对包括Cu(I)在内的杂化结构的整体分子结构的影响。利用CuX （X = Cl, Br， I，或CN）与五种结构相关的柔性有机配体（L1-L5）在水（溶剂）热条件下的自组装，我们合成并表征了10种结构独特的Cu(I)/X/ α， ω -双（苯并三唑）烷有机无机杂化族材料，{[CuCl](2)(L1)}(n) (1), {[cul](2)(L2)}(n) (2), {[cul](2)(L4)}(n) (4), {[cur](2)(L4)}(n) (5), {[cur](3)(L5)}(n) (6), {[CuCN](2)(L1)}(n)(7)。{[CuCl](4)(L2)}(n) (8), {[cur](4)(L2)}(n)(9)，和{[CuCl](2)(L4)}(n)（10）通过元素分析，x射线粉末衍射，傅里叶变换红外光谱，热重分析和光致发光测量。单晶X射线分析表明，这些化合物的无机亚基是{Cu(2)X(2)}双核团簇（1和2），{Cu(4)X(4)}立方团簇（4、5和10），{CuX}(n)单链（3和7），{Cu(3)X(3)}(n)阶梯链(6)和前所未有的{Cu(8)X(8)}(n)带状（8和9）。从一维（1-4）到二维（5和6）再到三维（7-10）的维数增加表明，双（苯并三唑）烷配体的间隔长度和异构性对Cu(I)杂化材料骨架的形成起着至关重要的作用。还探讨了反阴离子和π - π堆叠相互作用对这些杂化配位聚合物的形成和维数的影响。此外，所有配合物在室温下均表现出高的热稳定性和强的固体荧光性质。
This work focused on a systematic investigation of the influences of the spacer length of the flexible alpha,omega-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 (L1-L5) under hydro(solvo)thermal conditions, we have synthesized and characterized 10 structurally unique materials of the Cu(I)/X/alpha,omega-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 {Cu(2)X(2)} binuclear clusters (1 and 2), {Cu(4)X(4)} cubane clusters (4, 5, and 10), {CuX}(n) single chains (3 and 7), a {Cu(3)X(3)}(n) ladderlike chain (6), and unprecedented {Cu(8)X(8)}(n) ribbons (8 and 9). The increasing dimensionality from 1-D (1-4) to 2-D (5 and 6) to 3-D (7-10) 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 pi-pi 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.