【作者】 蒋正静；

【导师】 陆路德； 武晓东；

【作者基本信息】 南京理工大学 ， 化学工程与技术， 2009， 博士

【摘要】 N杂环化合物及其配合物、含稀土金属原子簇合物,由于它们在生命过程、光、电、磁、催化等领域具有诱人的应用前景,已成为无机化学和材料化学领域的研究热点之一。本文围绕当前关于配合物研究的若干热点,采用溶液合成、水热合成等方法,设计、合成并解析了15个配合物的单晶结构,其中10个为N杂环化合物的配合物,5个为含稀土金属的原子簇合物。运用NMR技术对其中2种N杂环化合物、3种N杂环配合物的溶液结构进行了研究,还运用量子化学计算对上述2种N杂环化合物溶液中的结构加以验证。对其中部分配合物的热稳定性等进行了研究。以异烟肼为配体与CuCN、CuI、PtI₄、FeSO₄等金属盐反应,得到了四种不同结构的配位化合物晶体,其中1个为二维结构配聚物、1个为一维结构配聚物、1个双核配合物,1个单核配合物,并用单晶X-射线衍射实验证实了它们的晶体结构。比较并分析了阴离子、中心离子的种类对配合物晶体结构的影响。运用NMR技术对CuCN的配合物在溶液中的行为进行了研究。对CuCN、CuI、PtI₄的配合物的热稳定性进行了研究,分析了其可能的热分解方式。以尼古丁与CuI、CuBr、HgI₂、HgBr₂等金属盐反应,得到了四种配位化合物晶体,其中2个为结构不同的四核簇合物、2个为同构的一维链状配聚物,它们的晶体结构得到了单晶X-射线衍射实验的证实。比较了CuI、CuBr形成配合物的反应方式,分析了CuI、HgI₂这两个具有相同的d¹⁰价电子组态,但属于不同周期,电荷与原子半径都不同的阳离子对配合物晶体结构的影响;对这两种配合物在溶液中的行为进行了研究;对CuI、HgI₂、HgBr₂的配合物的热稳定性进行了研究,分析了其可能的热分解方式。比较分析了以CuI为阳离子源、以同含有一个吡啶环、多个配位氮原子的异烟肼和尼古丁为配体,在相同反应条件下反应,得到了配位环境完全不同的配合物晶体的原因在于配体的侧基不同,异烟肼侧基为链状,而尼古丁侧基为环状,基团的大小、构型以及空间的位阻有显著的差异,配体为适应不同的配位环境,调整了配位方式及空间排列。利用水热合成方法,简单、快速地合成了2,2’-联吡啶-Cd、异烟酸-Co的完好的配合物晶体,并用单晶X-射线衍射实验对其晶体结构进行了证实。利用多种2D NMR技术,研究了另一类含N杂环化合物——盐酸氯丙嗪和盐酸异丙嗪在溶液中的结构,对盐酸氯丙嗪在DMS0-d₆、CD₃COCD₃、CDCl₃以及盐酸异丙嗪在DMSO-d₆、CDCl₃中的¹H-NMR和¹³C-NMR信号进行了准确的全归属,并对不同溶液中侧链信号的差异进行了分析,实验证实了盐酸氯丙嗪和盐酸异丙嗪在CDCl₃中均采取卷曲构象,推测分子中可能存在阳离子-π体系的相互作用。利用量子化学计算的方法对上述结论加以验证,结果相吻合。考察了稀土离子Pr³⁺,Dy³⁺对由其诱导的[MS₄]^2-（M＝Mo,W）和Ag⁺自组装反应产物结构的影响,获得了三个具有一维螺旋型阴离子链的原子簇聚合物,讨论了溶剂化平衡阳离子的不同对阴离子骨架构型晶胞的大小等的影响。还讨论了不同分子构造单元[MoS₄]²⁺和[WS₄]²⁺对阴离子骨架构型,晶胞大小等的影响。考察了AgI在溶剂化的稀土阳离子的诱导下的自组装反应,获得了一新型结构的簇聚物,表明由于I^-的配位多样性,可以带来配合物结构的多样性。以[W^V（CN）₈]^3-为分子构造单元,由溶剂化稀土阳离子诱导合成了一维链状簇聚物,说明稀土阳离子配位的多样性以及CN^-的强桥联配体作用对形成这种簇聚物有重要影响。更多还原

【Abstract】 N-heterocyclic compounds and their transition metal complexes and rare earth clusters have become one of the hot research topics in inorganic chemistry and material chemistry due to their attractive potential applications in the fields of life science,photochemistry, electrochemistry,magnetism as well as catalysis.With these in mind,a series of metal complexes have been designed and synthesized using general solution synthesis and hydrothermal synthesis.X-Ray single crystal diffraction has been performed on fifteen synthesized complexes and the single crystal structure determinations show that,among the fifteen complexes,ten are N-heterocyclic transition metal complexes and five are rare earth clusters.Based on NMR technique,the structures of two N-heterocyclic compounds and three N-heterocyclic metal complexes in solution have been investigated.In addition, the structures of the two N-heterocyclic compounds in solution,have been proved by quantum chemical calculations.The electrochemical properties and thermal properties of some of the synthesized metal complexes have also been studied.Reaction of isoniazid with CuCN,CuI,PtI₄ and FeSO₄ gave four complexes.X-Ray single crystal structure determinations carried out on these four complexes show that one is a two-dimensional（2D） coordination polymer,one is a one-dimensional（1D） coordination polymer,the third one is a dinuclear complex and the fourth one is a mononuclear complex.The influence of anions and central metal ions on crystal structures of the complexes has been studied and compared.Based on NMR technique,the structure of the complex of CuCN with isonicotinly hydrazide in solution has been investigated.In addition,the thermal stability of the complexes of CuCN、CuI、PtI₄ with isonicotinly hydrazide has been investigated and the possible thermal decomposition modes have been proposed.Reaction of nicotine with CuI、CuBr、HgI₂ and HgBr₂ yielded four complexes.X-Ray single crystal structure analysis carried out on these four complexes indicates that two of them are tetranuclear clusters and the other two are 1D chain-like coordination polymers. The coordination modes of CuI and CuBr with nicotine have been studied and compared with each other.In the cases of Cu⁺ and Hg²⁺ complexes,although Cu⁺ and Hg²⁺ ions have the same electronic configuration,d¹⁰,they belong to different rows and have different atomic charges and radius.These factors clearly influence the structures of their complexes with nicotine.The structures of CuI and HgI₂ with nicotine in solution have also been studied.For the complexes of CuI,HgI₂ and HgBr₂ with nicotine,their thermal stability has been analysed and the possible decomposition modes have also been proposed.Although isoniazid and nicotine have some similarities,for example,both ligands have a pyridine ring,there are significant differences between them:isoniazid has a bulky substituent（-CONHNH₂） atγposition but nicotine has a different bulky substituent （N-methylpyrrolidine） atβposition.These differences could have influence on the molecular strucutres of the complexes.X-Ray crystal structure determinations carried out on the complexes have clearly confirmed this.In fact,under the same reaction conditions, different molecular structures could be obtained by reacting CuI with isoniazid or nicotine. To summarize,the two ligands have different sizes,different conformations as well as different stereo hindrance,which make them adopt different coordination modes and different arrangements when forming the complexes with the ligands.Using hydrothermal syntheis,two complexes,2,2’-bipyridine-Cd²⁺ and isonicotinic acid-Co²⁺,have been obtained and their structures characterized by X-ray single crystal diffraction.Based on 2D NMR technique,the structures of other two N-heterocyclic compounds, chlorpromazine hydrochloride and promethazine hydrochloride,in solution have been investigated.All the ¹H-NMR and ¹³C-NMR peaks of chlorpromazine hydrochloride in DMSO-d₆,CD₃COCD₃ and CDCl₃ those of promethazine hydrochloride in DMSO-d₆ and CDCl₃ have been fully assigned.The differences between the peaks of side chains of the two N-heterocyclic compounds in different solvents have also been analyzed.The data showed that both compounds in CDCl₃ solution have folded conformations,which is probably due to the interactions between the cations andπsystem in the molecules.This is also consistent with the results obtained from the quantum chemical calculations carried out on these compounds.The roles of pr³⁺and Dy³⁺ ions have been discussed when they induced[MS4]^2-（M＝Mo,W） and Ag⁺ to form the three clusters with 1D helical anion-chain.The influence of the different solvated ions and the building blocks,[MoS₄]²⁺ and[WS₄]²⁺,on the conformations of the anion skeletons and the size of the unit cells has also been discussed.The self-assembly of AgI induced by the solvated rare earth ions has been studied and a new type of cluster was obtained.Comparison of the crystal structure of this cluster with the reported related structurally characterized clusters shows that the versatility of coordination modes of I^- anion can result in the versatility of structures of the clusters.Using[W^V（CN）₈]^3- as the building block,a 1D chain-like cluster has been synthesized by the induction of a solvated rare earth cation.The crystal strucutre of the cluster shows that in the presence of CN^- as a strong bridging ligand,the versatility of the coordination modes of rare earth cations has important influence on the formation of the clusters of this type.更多还原