水杨醛类双席夫碱的溶致变色性质及其半夹心铑、铱配合物的合成

发布时间：2018-11-13 10:27

【摘要】：席夫碱是一类重要的含N化合物,其亚胺基团(-C=N-)中的N上含有孤对电子,可以与大部分金属离子形成稳定的配合物。一些双齿席夫碱可以通过[N,N]、[N,O]、[N,C]、[N,S]与金属离子进行配位,构建出丰富的空间结构,使得席夫碱及其配合物具有各种性质与功能,在医学、催化、传感、光学等领域有着广泛的应用。本文利用水杨醛与对苯二胺、联苯胺、邻联甲苯胺、4,4′-二氨基二苯甲烷反应,构建出一系列双齿席夫碱。利用此类席夫碱含有双官能团的结构(含-OH,-C=N-),通过[N,O]与金属离子铑、铱配位,构建出一系列席夫碱桥联的双核铑、铱等配合物,为以后合成大环类铑、铱配合物做了前期工作。本文首先合成了具有O,N-给体的双齿席夫碱[{(2-OH)C6H4CH=N}2R]{R=C6H4,L1;R=(C6H4)2,L2;R=(o-MeC6H3)2,L3;R=(C6H4)2CH2,L4},通过紫外可见光谱和荧光光谱测试了它们在不同溶剂下的光谱性质。通过对L1、L2、L3、L4熔点、红外光谱、核磁氢谱的测定和对化合物L1单晶结构的测试,证实得到了一系列水杨醛衍生的双席夫碱。其次,合成了氯桥联铑、铱配合物[Cp*MCl2]2(M=Rh,1;Ir,2),然后让其与席夫碱进行反应生成双核的铑、铱配合物。实验时先把水杨醛类席夫碱加入甲醇溶剂中与氢氧化钠反应除去酚羟基的氢,形成活泼的O-离子;把配合物1、2分别溶解在CH2Cl2溶剂中,过滤至上述反应中,合成了半夹心结构的铑、铱配合物[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2C6H4](M=Rh,1a;Ir,1b),[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2(C6H4)2](M=Rh,2a;Ir,2b),[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2(o-MeC6H3)2](M=Rh,3a;Ir,3b),[(Cp*MCl)2{N,O-κ2-(2-O)C6H4CH=N}2(C6H4)2CH2](M=Rh,4a;Ir,4b)我们将以上所得的配合物1a,2a,3a,4a;1b,2b,3b,4b均作了红外光谱和核磁氢谱的测定,并对特征峰进行了归属。此外,我们还对配合物1a进行了X-射线单晶衍射表征,通过晶体数据的研究,确认我们合成出了一系列新型的双核铑、铱配合物。此类配合物易溶于二氯甲烷和氯仿等有机溶剂中,为研究此类配合物各种性质提供了有利条件。同时我们通过改变席夫碱配体链的长短对双核类铑、铱配合物的空间结构进行调控,这对一系列新型的大环类铑、铱配合物的构筑,提供了很好的模板,具有广阔的研究前景。
[Abstract]:Schiff base is an important class of N-containing compounds. The N of the iminodium group (-Cn-) contains solitary pairs of electrons, which can form a stable complex with most metal ions. Some didentate Schiff bases can be coordinated with metal ions by [Nn], [No], [NZC], [NZS], and form rich spatial structures, which make Schiff bases and their complexes have various properties and functions. In medicine, catalysis, sensing, optics and other fields have a wide range of applications. In this paper, a series of didentate Schiff bases were synthesized by the reaction of salicylaldehyde with p-phenylenediamine, benzidine, o-bimethylaniline, 4o 4- diaminodiphenylmethane. A series of binuclear rhodium and iridium complexes bridged by Schiff bases were synthesized by [Nino O] coordination with metal ions rhodium and iridium (including-OH,-C=N-), which were used for the synthesis of macrocyclic rhodium, and the structure of Schiff base containing bifunctional groups (including-OH,-C=N-) was used to construct a series of binuclear rhodium and iridium complexes bridged by Schiff bases. The iridium complex has done the preliminary work. In this paper, we first synthesized the didentate Schiff base with ON- donor [{(2-OH) C6H4CH=N} 2R] {RZC _ 6H _ 4N _ L _ 1C ~ (1 +) R = (C6H4) _ 2C _ (2) L _ (2N) R = (o-MeC6H3) ~ (2) L _ (3); R = (C6H4) 2CH _ 2C _ 4}. Their spectral properties in different solvents were measured by UV-Vis and fluorescence spectra. A series of bis Schiff bases derived from salicylidene aldehyde have been obtained by the determination of melting point, infrared spectrum, nuclear magnetic hydrogen spectrum and single crystal structure of compound L1. Secondly, chlorine-bridged rhodium and iridium complexes [Cp*MCl2] 2 (Cp*MCl2 1, Ir2) were synthesized, and then reacted with Schiff base to form binuclear rhodium and iridium complexes. In the experiment, salicylic aldehyde Schiff base was added into methanol solvent to react with sodium hydroxide to remove phenolic hydroxyl hydrogen to form active O- ion. The complex 1t2 was dissolved in the CH2Cl2 solvent and filtered into the above reaction. The semi-sandwich rhodium and iridium complexes [(Cp*MCl) 2 {NnO- 魏 2- (2-O) C6H4CH=N} 2C6H4] (Mnrh 1 a) were synthesized. (Ir,1b), [(Cp*MCl) 2 {NGUO- 魏 2- (2-O) C6H4CH=N} 2 (C6H4) 2], [(Cp*MCl) 2 {NGUO- 魏 2- (2-O) C6H4CH=N} 2 (o-MeC6H3) 2] (Mnhh 3aa), [(Cp*MCl) 2 {NGUO- 魏 2- (2-O) C6H4CH=N} 2 (o-MeC6H3) 2], [(Cp*MCl) 2 {NGO- 魏 2- (2-O) C6H4CH=N} 2 (o-MeC6H3) 2]; (Ir,3b), [(Cp*MCl) 2 {NO- 魏 2- (2-O) C6H4CH=N} 2 (C6H4) 2CH2] The infrared spectra and nuclear magnetic hydrogen spectra were measured for 1b ~ (2) b ~ (2) B ~ (3) B ~ (4) and the characteristic peaks were assigned. In addition, the complex 1a has been characterized by X-ray single crystal diffraction, and a series of new binuclear rhodium and iridium complexes have been synthesized by the study of crystal data. These complexes are easily soluble in organic solvents such as dichloromethane and chloroform, which provides favorable conditions for studying the properties of these complexes. At the same time, we regulate the spatial structure of binuclear rhodium and iridium complexes by changing the length of Schiff base ligand, which provides a good template for the construction of a series of new macrocyclic rhodium and iridium complexes, and has a broad research prospect.
【学位授予单位】：辽宁大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.1

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