Luminescent zinc and cadmium complexes incorporating 1,3,5-benzenetricarboxylate and a protonated kinked organodiimine: From a hydrogen-bonded layer motif to thermally robust two-dimensional coordination polymers
Luminescent zinc and cadmium complexes incorporating 1,3,5-benzenetricarboxylate and a protonated kinked organodiimine: From a hydrogen-bonded layer motif to thermally robust two-dimensional coordination polymers
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DOI：
10.1016/j.jssc.2007.04.010
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发表时间：
2007-06
影响因子：
3.3
通讯作者：
Maxwell A. Braverman;R. M. Supkowski;R. LaDuca
中科院分区：
文献类型：
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作者：
Maxwell A. Braverman;R. M. Supkowski;R. LaDuca
以氯化锌、1，3，5-苯三甲酸（H3 BTC）和4，4 ′-联吡啶胺（dpa）为原料，通过水热反应合成了两种不同的配合物，并通过单晶X射线衍射、红外光谱和元素分析对其进行了表征。在酸性条件下，分离出分子式为[Zn（HBTC）2（Hdpa）2]（1）的离散中性分子物种，其聚集成二维氢键层。在更碱性的条件下，得到了二维层状配位聚合物[Zn（BTC）（Hdpa）]（2），它表现出[Zn（BTC）（Hdpa）]蛇形链基序共价连接成3个相连的起伏的4.82拓扑二维层。1和2在Zn处具有四面体配位。在合成中使用硝酸镉产生[Cd（BTC）（H2O）（Hdpa）]（3），其显示与2类似的层拓扑结构，但具有由Cd处的八面体配位赋予的显著调整。在所有情况下，由Hdpa配体促进的超分子氢键提供了重要的辅助结构导向作用。所有材料在用紫外光激发时显示蓝色发光，归因于配体内跃迁。晶体学数据：一曰：单斜晶系，C2/c，a=25.389（6）°，B=9.811（2）°，c=17.309（4）°，β=128.957（3）°，2：单斜晶系，P21/c，a=13.212（17）c，B=17.15（2）°，c=7.506（10）°，β=93.71（2）°，3：单斜晶系，C2/c，a=14.241（6）°，B=15.218（6）°，c=17.976（7）°，β=109.330（6）°。
Hydrothermal treatment of zinc chloride, 1,3,5-benzenetricarboxylic acid (H3BTC), and 4,4′-dipyridylamine (dpa) afforded two different complexes depending on reaction conditions, which were characterized by single-crystal X-ray diffraction, infrared spectroscopy, and elemental analysis. Under acidic conditions, a discrete neutral molecular species with formulation [Zn(HBTC)2(Hdpa)2] (1) was isolated, which aggregates into two-dimensional hydrogen-bonded layers. Under more basic conditions, the two-dimensional layered coordination polymer [Zn(BTC)(Hdpa)] (2) is obtained, which manifests covalent linkage of [Zn(BTC)(Hdpa)] serpentine chain motifs into 3-connected undulating 4.82topology 2-D layers. Both 1 and 2 possess tetrahedral coordination at Zn. Use of cadmium nitrate in the synthesis resulted in [Cd(BTC)(H2O)(Hdpa)] (3), which displays a similar layer topology as 2 but with significant adjustments imparted by octahedral coordination at Cd. In all cases, supramolecular hydrogen bonding promoted by Hdpa ligands provide an important assistive structure-directing role. All materials display blue luminescence upon excitation with ultraviolet light, ascribed to intraligand transitions. Crystallographic data: 1: monoclinic, C2/c, a=25.389(6)Å, b=9.811(2)Å, c=17.309(4)Å, and β=128.957(3)°, 2: monoclinic, P21/c, a=13.212(17)c, b=17.15(2)Å, c=7.506(10)Å, and β=93.71(2)°, and 3: monoclinic, C2/c, a=14.241(6)Å, b=15.218(6)Å, c=17.976(7)Å, and β=109.330(6)°.