Jess Inke, Taborsky Petr, Pospísil Jirí, Näther Christian
Institut für Anorganische Chemie der Christian-Albrechts-Universität zu Kiel, Olshausenstrasse 40, D-24098 Kiel, Germany.
Dalton Trans. 2007 Jun 14(22):2263-70. doi: 10.1039/b701905j. Epub 2007 Apr 30.
Three new coordination polymers based on CuI and 2,3-dimethylpyrazine (2,3-dmpyz) were prepared, structurally characterized and investigated for their thermal and luminescence properties. In the ligand rich 2:3 compound [(CuI)2(2,3-dmpyz)3] (CuI)2 dimers are found, which are connected by the N-donor ligands into chains, whereas in the structure of the 1:1 intermediate [(CuI)(2,3-dmpyz)] (CuI)4 tetramers are found, which are also connected into chains. The crystal structure of the ligand deficient 2:1 compound [(CuI)2(2,3-dmpyz)] is built up of CuI double chains, which are connected by the 2,3-dmpyz ligands into layers. Thermal decomposition of results in its direct transformation into the ligand deficient compound , without the formation of the 1:1 compound as an intermediate. A similar thermal reactivity is found for compound , which transforms into on heating. Stirring of a crystalline suspension of pure or in acetonitrile, always leads to a transformation into the ligand deficient compound indicating that compound is the most stable of all the coordination polymers, whereas compounds and are metastable. The luminescence properties of the CuCl and CuI coordination polymers were investigated at 298 and 77K. It was observed that the emission maxima strongly depends on the nature of the halide atom and the composition and structure of the coordination polymers. In addition, several of these compounds show luminescence thermochromism. These results are compared with those obtained for the previously reported CuCl and CuBr(2,3-dimethylpyrazine) coordination polymers.
制备了三种基于碘化亚铜（CuI）和2,3 - 二甲基吡嗪（2,3 - dmpyz）的新型配位聚合物，对其进行了结构表征，并研究了它们的热性能和发光性能。在配体丰富的2:3化合物[(CuI)2(2,3 - dmpyz)3]中发现了(CuI)2二聚体，它们通过氮供体配体连接成链，而在1:1中间体[(CuI)(2,3 - dmpyz)]的结构中发现了(CuI)4四聚体，它们也连接成链。配体不足的2:1化合物[(CuI)2(2,3 - dmpyz)]的晶体结构由CuI双链组成，这些双链通过2,3 - dmpyz配体连接成层。其热分解导致直接转化为配体不足的化合物，没有形成1:1化合物作为中间体。化合物也有类似的热反应性，加热时会转化为。将纯的或在乙腈中的晶体悬浮液搅拌，总是会导致转化为配体不足的化合物，这表明化合物是所有配位聚合物中最稳定的，而化合物和是亚稳的。在298K和77K下研究了氯化铜（CuCl）和碘化亚铜（CuI）配位聚合物的发光性能。观察到发射最大值强烈依赖于卤原子的性质以及配位聚合物的组成和结构。此外，这些化合物中的几种表现出发光热致变色。将这些结果与先前报道的氯化铜（CuCl）和溴化铜（CuBr）(2,3 - 二甲基吡嗪)配位聚合物所获得的结果进行了比较。
