【作者】 王军杰；

【导师】 卜显和；

【作者基本信息】 南开大学 ， 物理化学， 2010， 博士

【摘要】 非配位基团作为配体的重要组成部分,不但对金属配合物的构筑具有重要作用,而且还会对配合物的性质产生决定性影响。这方面的研究对控制相关配体向具有特定结构和功能的金属配合物的定向组装具有重要意义。本论文选择几类有代表性的配体,研究了非配位基团在构筑金属配合物过程中的作用。合成了一系列具有零维、一维、二维或三维结构的配合物,解析了它们的结构,研究了配合物的电子顺磁共振光谱(EPR)、磁性、紫外可见和荧光性能。具体内容如下：一、合成并表征了具有蒽基骨架的双羧酸及其相关配体(9,10-蒽二甲酸H2L1,1,5-葸二甲酸H2L2,1,8-蒽二甲酸H2L3,蒽醌L4,1,8-二氰基葸醌L5,1,5-葸醌二甲酸H2L6,1,5-蒽醌二甲酸H2L7及1,2,3-苯三甲酸H3L8),并结合不同的辅助配体(4,4’-联吡啶L9,1,10-邻菲咯啉L10和1,3-二(4-吡啶基)丙烷L11),制备了AgⅠ,MnⅡ,ZnⅡ和CdⅡ等11个新型配合物,解析了它们的结构。此外,还对ZnⅡ和CdⅡ系列配合物的室温固态荧光性能进行了研究。二、选择五个具有不同骨架的单羧酸配体(9-菲酸HL12,2-苯基喹啉-4-酸HL13,1-金刚烷酸HL14,4-苯基苯甲酸HL15和3,3-二苯基丙酸HL16),并结合不同的辅助配体(4,4’-联吡啶L9,1,10-邻菲咯啉L10,2,2’-联吡啶L17,1,4-二氮环[2.2.2]辛烷L18,吡嗪L19,六次甲基四胺L20,1,4-二氮环庚烷L21和3-(2-吡啶基)吡唑HL22),合成了CuⅡ、ZnⅡ、CdⅡ、MnⅡ、CoⅡ和NiⅡ等23个金属配合物,解析了它们的结构。另外,分别对CuⅡ系列、ZnⅡ和CdⅡ系列及MnⅡ和CoⅡ系列配合物的固体电子顺磁共振光谱(EPR)、荧光和磁学性能进行了研究。三、合成、表征了三个以吡啶环和苯并咪唑环为基本骨架的含氮杂环配体(2-(苯并吡唑-1-甲基)吡啶L24,2-(苯并吡唑-1-甲基)吡啶L25和2-(苯并吡唑-1-甲基)吡啶L26),制备了ZnⅡ、CdⅡ和HgⅡ等5个新型配合物,解析了它们的结构。另外,在ZnⅡ和HgⅡ系列配合物中研究了它们在室温下的固体紫外可见光谱和固态荧光光谱。结果表明非配位基团对配合物的结构和性能具有重要影响。更多还原

【Abstract】 Non-coordinating group, as an important part of the ligand, can not only play an important role in the formation of complexes, but also can exert a deciding influence on their structures and functions (or properties).In this dissertation, Some representative ligands with non-coordination groups were designed and synthesized, and a series of metal complexes with 0D, 1D,2D or 3D structures had been obtained and characterized. The rules of non-coordination groups in governing the framework’s formations of these complexes were studied. Furthermore, EPR spectra, luminescence and magnetic properties of some complexes have been discussed. The main contents have been summarized as follows:1. Eleven AgⅠ, MnⅡ, ZnⅡand CdⅡcomplexes with anthracene-based dicarboxylate and structurally related ligands (anthracene-9,10-dicarboxylic acid H2L1, anthracene-1,5-dicarboxylic acid H2L2, anthracene-1,8-dicarboxylic acid H2L3, anthracene-9,10-dione L4, 9,10-dioxo-9,10-dihydroanthracene-1,8-dicarbonitrile L5, 9,10-dioxo-9,10-dihydroanthracene-1,8-dicarboxylic acid H2L6, 9,10-dioxo-9,10-dihydroanthracene-1,5-dicarboxylic acid H2L7 and benzene-1,2,3-tricarboxylic acid H3L8) and corresponding auxiliary ligands (4,4’-bipyridine L9, 1,10-phenanthroline L10 and 1,3-di(4-pyridyl)propane L11) were synthesized and characterized. Moreover, the luminescent properties of the ZnⅡand CdⅡcomplexes and the corresponding ligands have been investigated at room temperature.2. Five carboxylic acids bearing different bulky skeletons (phenanthrene-9-carboxylic acid HL12,2-phenylquinoline-4-carboxylic acid HL13, adamantane-1-carboxylic acid HL14, biphenyl-4-carboxylic acid HL15 and 3,3-diphenylpropanoic acid HL16)and their twenty three CuⅡ, ZnⅡ, CdⅡ, MnⅡ, CoⅡand NiⅡcomplexes were designed and synthesized with corresponding auxiliary ligands (4,4’-bipyridine L9, 1,10-phenanthroline L10, 2,2’-bipyridine L17, 1,4-diazabicyclo[2.2.2]octane L18, pyrazine L19, hexamethylenetetramine L20, 1,4-diazepane L21 and 3-(2-pyridyl)pyrazole HL22). Furthermore, the EPR spectra of the CuⅡcomplexes and the magnetic properties of the MnⅡand CoⅡcomplexes have been studied. And the luminescent properties of the ZnⅡand CdⅡcomplexes and the corresponding ligands have also been investigated at room temperature.3. Three N-donor ligands with benzimidazole and pyridine rings (l-(2-pyridylmethyl)-1#-benzimidazole L24, 1-(3-pyridylmethyl)-1H-benzimidazole L25 and 1-(4-pyridylmethyl)-1H-benzimidazole L26) were designed and synthesized. Five ZnⅡ, CdⅡand HgⅡcomplexes have been synthesized and structurally characterized. Moreover, the UV-Vis and luminescent spectra of the ZnⅡand HgⅡcomplexes and the corresponding ligands have been investigated at room temperature.The results show that the non-coordination group plays an important role in affecting the structures and properties of complexes.更多还原