固态研磨控制下的金属有机盐及其配合物的合成和可逆转化
发布时间：2019-01-17 10:11
【摘要】：二次球形配位是指金属配合物与质子化有机配体通过分子间相互作用形成的超分子配位物。近年来,基于二次配位构筑的超分子化合物在分子识别,分离与提取,催化等领域开始得到越来越多的关注。但是基于二次球形配位的固态反应研究工作尚少,仍亟待深入研究。基于此,本论文开展了如下工作。本文合成了有机含氮双齿配体,(±)-N,N'-二苄基-反式-1,2-环己二胺(L),利用质子化配体L和金属氯化物,在不同溶剂的条件的控制下合成了二次配位的超分子化合物[H2L]~(2+)·[CuCl_4]2 (晶体1)和[H2L]~(2+)·[ZnCl_4]~(2-) (晶体2)。同时采用固态合成方法,即将质子化配体L与CuCl_2,滴加一滴盐酸进行酸化,在微量溶剂辅助的直接研磨下,也可以直接制备上述金属氢键盐。对上述得到的二次配位金属氢键盐与其配合物进行了固态转化研究,即金属氢键盐在加入强碱KOH,微量溶剂辅助研磨5分钟左右。在加热的条件下,脱HCl气体,直接转化为配合物[(CuCl_2)(L)](晶体1'),[(ZnCl_2)(L)](晶体2');同时,配合物[(CuCl_2)(L)](晶体1'),[(ZnCl_2)(L)](晶体2')在相应的溶剂和盐酸的氛围中,也可以直接转化为相应的二次配位金属氢键盐晶体1和晶体2。此外,本文研究了含氮有机双齿配体,(±)-N,N'-二苄基-反式-1,2-环己二胺与其它金属氯化物作用得到H2O(?)[H2L]~(2+).[CdC14]~(2-)(晶体3),H2O(?)[H2L]~(2+)·[CoCl_4]~(2-)(晶体 4)和 EtOH(?)[H2L]~(2+).[CuC14]~(2-)(晶体 5)并且研究它们的晶体结构及其固体荧光性质。
[Abstract]:Secondary spherical coordination refers to the supramolecular coordination formed by the interaction between metal complexes and protonated organic ligands. In recent years, supramolecular compounds based on secondary coordination have attracted more and more attention in the fields of molecular recognition, separation and extraction, catalysis and so on. However, the study of solid state reaction based on secondary spherical coordination is still few, and it is still in need of further study. Based on this, this paper has carried out the following work. The organic nitrogen-containing didentate ligands, (卤) -N ~ (-) -dibenzylidene-trans-1 ~ (2) -cyclohexanediamine (L), have been synthesized by using proton ligand L and metal chloride. The supramolecular compounds [H _ 2L] ~ (2) [CuCl_4] _ 2 (crystal 1) and [H _ 2L] ~ (2) [ZnCl_4] ~ (2-) (crystal 2) were synthesized under different solvent conditions. At the same time, the proton ligand L and CuCl_2, were dripped with a drop of hydrochloric acid for acidification by solid state synthesis, and the metal hydrogen bonded salts could also be directly prepared by direct grinding with the aid of a small amount of solvent. The solid state transformation of the second coordination metal hydrogen bond salt with its complex was studied, that is to say, the metal hydrogen bond salt was ground for about 5 minutes with the addition of a strong alkali KOH, trace solvent. Under the heating condition, the HCl gas is removed and transformed directly into complexes [(CuCl_2) (L)] (crystal 1'), [(ZnCl_2) (L)] (crystal 2'); At the same time, the complexes [(CuCl_2) (L)] (crystal 1'), [(ZnCl_2) (L)] (crystal 2') in the corresponding solvent and hydrochloric acid atmosphere, It can also be directly converted into the corresponding secondary coordination metal hydrogen bonded salt crystal 1 and crystal 2. In addition, we have studied the reaction of nitrogen-containing organic didentate ligand, (卤) -N- (N-) -dibenzyl-trans-1- (2-cyclohexanediamine) with other metal chlorides to obtain H _ 2O [H _ 2L] ~ (2). [CdC14] ~ (2-) (crystal 3), [H _ 2L] ~ (2), [CdC14] ~ (2-) (crystal 3), H2O [H _ 2L] ~ (2) [CoCl_4] ~ (2-) (crystal 4) and EtOH (?) [H _ 2L] ~ (2). [CuC14] ~ (2-) (crystal 5) and their crystal structure and solid fluorescence properties were studied.
【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
本文编号：2409949
[Abstract]:Secondary spherical coordination refers to the supramolecular coordination formed by the interaction between metal complexes and protonated organic ligands. In recent years, supramolecular compounds based on secondary coordination have attracted more and more attention in the fields of molecular recognition, separation and extraction, catalysis and so on. However, the study of solid state reaction based on secondary spherical coordination is still few, and it is still in need of further study. Based on this, this paper has carried out the following work. The organic nitrogen-containing didentate ligands, (卤) -N ~ (-) -dibenzylidene-trans-1 ~ (2) -cyclohexanediamine (L), have been synthesized by using proton ligand L and metal chloride. The supramolecular compounds [H _ 2L] ~ (2) [CuCl_4] _ 2 (crystal 1) and [H _ 2L] ~ (2) [ZnCl_4] ~ (2-) (crystal 2) were synthesized under different solvent conditions. At the same time, the proton ligand L and CuCl_2, were dripped with a drop of hydrochloric acid for acidification by solid state synthesis, and the metal hydrogen bonded salts could also be directly prepared by direct grinding with the aid of a small amount of solvent. The solid state transformation of the second coordination metal hydrogen bond salt with its complex was studied, that is to say, the metal hydrogen bond salt was ground for about 5 minutes with the addition of a strong alkali KOH, trace solvent. Under the heating condition, the HCl gas is removed and transformed directly into complexes [(CuCl_2) (L)] (crystal 1'), [(ZnCl_2) (L)] (crystal 2'); At the same time, the complexes [(CuCl_2) (L)] (crystal 1'), [(ZnCl_2) (L)] (crystal 2') in the corresponding solvent and hydrochloric acid atmosphere, It can also be directly converted into the corresponding secondary coordination metal hydrogen bonded salt crystal 1 and crystal 2. In addition, we have studied the reaction of nitrogen-containing organic didentate ligand, (卤) -N- (N-) -dibenzyl-trans-1- (2-cyclohexanediamine) with other metal chlorides to obtain H _ 2O [H _ 2L] ~ (2). [CdC14] ~ (2-) (crystal 3), [H _ 2L] ~ (2), [CdC14] ~ (2-) (crystal 3), H2O [H _ 2L] ~ (2) [CoCl_4] ~ (2-) (crystal 4) and EtOH (?) [H _ 2L] ~ (2). [CuC14] ~ (2-) (crystal 5) and their crystal structure and solid fluorescence properties were studied.
【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
【参考文献】
相关硕士学位论文 前1条
1 李磊;N,N,N',N'-四苄基—萘-1,5-二胺的同质多晶现象及其构筑的二次球形超分子包结化合物[D];辽宁大学;2012年
，本文编号：2409949
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