苯并咪唑金属配合物有序超分子的合成与结构研究

【作者】 曹磊；

【导师】 李宁； 徐端钧；

【作者基本信息】 浙江大学 ， 物理化学， 2005， 硕士

【摘要】 过渡金属配合物在生物功能模拟和新型材料开发方面有着十分广阔的应用前景,研究过渡金属配合物的分子结构以及分子有序聚集而成的超分子结构,有助于深刻认识这些物质的性质。本论文重点探讨过渡金属配合物分子的有序聚集问题,从晶体结构的角度出发,用可靠的实验数据对羧基的配位方式和聚集体的聚集方式进行了分析讨论。 本论文选择一缩二二乙醇酸和硫二乙酸作为阴离子配体,选择可能形成芳环堆积的苯并咪唑(BZIM)作为中性配体,合成了一系列过渡金属配合物,并对得到的四个配合物聚集体的单晶进行了X射线结构分析(Table 1)。 这一系列新配合物的结构研究,得到以下有价值的结论: 1.在本文的一个晶体结构中,相互平行的苯并咪唑分子近距离地重叠堆积,苯并咪唑间距显著地小于芳环Van der Waals厚度,存在着显著的芳环堆积现象,说明芳环堆积作用是配合物形成过程中的一种超分子作用。 2.分子间氢键作用网络存在于本文所有的配合物结构中,除了传统的O—H…O、O—H…N这种形式的氢键以外,分子间C—H…O类型的弱氢键也比较普遍地出现在本文的结构中,氢键作用在超分子形成过程中起着重要作用。 3.本文中有三个晶体结构中并没有出现芳环堆积现象,因此配合物的聚合方式以及分子间氢键的存在对于能否形成芳环堆积都有着很重要的影响。更多还原

【Abstract】 The studies on transitional metal complexes are much interested whether as mimics of the biological system or as new materials with novel electrical, magnetic and optical properties. In terms of crystal structure, we analyzed the coordination modes of carboxyl groups and aggregate mode with credible experiment data.In this thesis, we choose the anion ligands (Diglycolic acid and Thiodiglycolic acid) and the neutral benzimidazole ligands (BZIM), which form aromatic stacking possibly, to synthesize a series of transition metal complexes (not reported), and four single crystals were determined by single crystal X-ray diffraction (Table 1).The following are the valuable results from our structure research of the series new complexes:1. In one crystal structure of the thesis, we found that the parallel benzimidazoles overlap and stack in close quarters, with the distance between benzimidazole less than the aromatic Van der Waals thickness. It shows the existence of aromatic π-π-stacking interaction. There are aromatic π-π-stacking interactions in the series complexes, which provide the strong evidence for aromatic π-π-stacking interactions being primary supramolecular action in the forming of orderly congeries.2. Extensive hydrogen bonds are in all the supramolecular systems. Besides traditional formation of O—H…O、 O-H… N, the type of feeble hydrogen bonds (C-H… O) exists at large comparably in the complexes. Hydrogen bonds play big roles in the formation of orderly congeries.3. In the other three structures of this thesis, there is no aromatic n-7i-stacking interaction. So we found that the forming of aromatic π-π-stacking interaction has important relation with the intermolecular hydrogen bonds and polymeric mode of complex.更多还原