固態(tài)研磨控制下的金屬有機(jī)鹽及其配合物的合成和可逆轉(zhuǎn)化
發(fā)布時(shí)間：2019-01-17 10:11
【摘要】：二次球形配位是指金屬配合物與質(zhì)子化有機(jī)配體通過分子間相互作用形成的超分子配位物。近年來,基于二次配位構(gòu)筑的超分子化合物在分子識(shí)別,分離與提取,催化等領(lǐng)域開始得到越來越多的關(guān)注。但是基于二次球形配位的固態(tài)反應(yīng)研究工作尚少,仍亟待深入研究�；诖�,本論文開展了如下工作。本文合成了有機(jī)含氮雙齒配體,(±)-N,N'-二芐基-反式-1,2-環(huán)己二胺(L),利用質(zhì)子化配體L和金屬氯化物,在不同溶劑的條件的控制下合成了二次配位的超分子化合物[H2L]~(2+)·[CuCl_4]2 (晶體1)和[H2L]~(2+)·[ZnCl_4]~(2-) (晶體2)。同時(shí)采用固態(tài)合成方法,即將質(zhì)子化配體L與CuCl_2,滴加一滴鹽酸進(jìn)行酸化,在微量溶劑輔助的直接研磨下,也可以直接制備上述金屬氫鍵鹽。對(duì)上述得到的二次配位金屬氫鍵鹽與其配合物進(jìn)行了固態(tài)轉(zhuǎn)化研究,即金屬氫鍵鹽在加入強(qiáng)堿KOH,微量溶劑輔助研磨5分鐘左右。在加熱的條件下,脫HCl氣體,直接轉(zhuǎn)化為配合物[(CuCl_2)(L)](晶體1'),[(ZnCl_2)(L)](晶體2');同時(shí),配合物[(CuCl_2)(L)](晶體1'),[(ZnCl_2)(L)](晶體2')在相應(yīng)的溶劑和鹽酸的氛圍中,也可以直接轉(zhuǎn)化為相應(yīng)的二次配位金屬氫鍵鹽晶體1和晶體2。此外,本文研究了含氮有機(jī)雙齒配體,(±)-N,N'-二芐基-反式-1,2-環(huán)己二胺與其它金屬氯化物作用得到H2O(?)[H2L]~(2+).[CdC14]~(2-)(晶體3),H2O(?)[H2L]~(2+)·[CoCl_4]~(2-)(晶體 4)和 EtOH(?)[H2L]~(2+).[CuC14]~(2-)(晶體 5)并且研究它們的晶體結(jié)構(gòu)及其固體熒光性質(zhì)。
[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, (鹵) -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, (鹵) -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.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.1
本文編號(hào)：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, (鹵) -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, (鹵) -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.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.1
【參考文獻(xiàn)】
相關(guān)碩士學(xué)位論文 前1條
1 李磊;N,N,N',N'-四芐基—萘-1,5-二胺的同質(zhì)多晶現(xiàn)象及其構(gòu)筑的二次球形超分子包結(jié)化合物[D];遼寧大學(xué);2012年
，本文編號(hào)：2409949
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