以雙亞胺酚基之銅、鎳錯合物製備混金屬配位化合物之合成、結構鑑定與性質研究

Synthesis, Structures, Characterization of Mixed Metal–Organic Coordination Compounds with Bis(salicyaldiminato)copper(ΙΙ) or Bis(salicyaldiminato)nickel(ΙΙ) as Metalloligands

張瀞云(Ching-Yun Chang)

指導教授 ： 吳景雲

國立暨南國際大學/科技學院/應用化學系/碩士(2014年)

摘要

本論文以H4salendc與二價銅、鎳金屬離子錯合反應合成出金屬化配位基，並以溶劑熱及自組裝合成法製備出一系列的無機超分子化合物，進而探討其固態結構及物理性質。
本論文首先利用H2LCu與金屬鹽類ZnCl2在含有KOH或CsOH之水溶液下進行溶劑熱反應合成配位聚合物 [K2Zn4(O)(LCu)4] (1)和[Cs2Zn4(O)(LCu)4] (1Cs)，為具有孔洞特性的三維鑽石型結構。
本論文以金屬化配位基(H2LM, M = Cu, Ni)與Zn(2,2ʹ-bipy)Cl2、Zn(1,10-phen)Cl2在室溫下進行自組裝合成，得到一系列混金屬配位化合物[Zn(2,2′-bipy)(LCu)]∙4H2O∙CH3OH (2)、[Zn(2,2′-bipy)(H2O)2(LCu)]∙7H2O (3)、{[Zn(2,2ʹ-bipy)]2(H2O)(LCu)2}•9.5H2O (4)、[Zn(2,2ʹ-bipy)(LCu)]•3.5H2O (5)、[Zn(1,10-phen)(H2O)2(LCu)]∙5.5H2O (6)、[Zn(2,2′-bipy)(H2O)2(LNi)]∙7H2O (7)、[Zn(1,10-phen)(H2O)2(LNi)]∙7.5H2O (8)。化合物2、化合物4和化合物5為一維線性之配位聚合結構，化合物3與化合物6-8為零維單體結構。
最後，本論文以有機配子H2L2與二價鋅金屬進行溶劑熱反應得到化合物[Zn(L2)(H2O)] (9)，為一維鋸齒狀結構。化合物9進行溶劑的吸附(脫附)實驗，可得知化合物9具有可逆的吸附(脫附)水分子的能力。再將化合物9進行陽離子置換反應，可得知化合物9之鋅離子可與銅、鎳離子置換。

關鍵字

亞胺基 ； 混金屬配位化合物 ； 溶劑熱合成法 ； 配位聚合物

並列摘要

Two metalloligands [M(H2salendc)] (M = Cu, Ni), have been prepared. Reaction of [Cu(H2salendc)] and ZnCl2 in the presence of KOH or CsOH under hydro(solvo)thermal conditions afforded mixed metal-organic coordination polymers (M′MOCPs) [K2Zn4(O)(LCu)4] (1, LCu = [Cu(salendc)]2‒) and [Cs2Zn4(O)(LCu)4] (1Cs). M′MOCPs 1 and 1Cs have identical crystal structures that feature a K+‒ or Cs+‒locked 4‒fold interpenetrating diamondoid network created by distorted tetrahedral Zn4O(O2C)8 secondary building units.
On the other hand, the slow diffusion reactions of [M(H2salendc)] (M = Cu, Ni) and Zn(N͡N)Cl2 (N͡N = 2,2′-bipy, 1,10-phen) afforded coordination complexes [Zn(2,2′-bipy)(LCu)]∙4H2O∙CH3OH (2), [Zn(2,2′-bipy)(H2O)2(LCu)]∙7H2O (3), {[Zn(2,2ʹ-bipy)]2(H2O)(LCu)2}•9.5H2O (4), [Zn(2,2ʹ-bipy)(LCu)]•3.5H2O (5), [Zn(1,10-phen)(H2O)2(LCu)]∙5.5H2O (6), [Zn(2,2′-bipy)(H2O)2(LNi)]∙7H2O (7), [Zn(1,10-phen)(H2O)2 (LNi)]∙7.5H2O (8). Complexs 2, 4 and 5 have 1D chain structure while complexs 3 and 6-8 are discrete structures.
In addition, we have also designed a monosalicylidene imine ligand H2L2. Assembly of H2L2 and Zn(OAc)2 under htdro(solvo)thermal conditions afforded MOCP [Zn(L2)(H2O)](9) adopting 1D zigzag chain structure. MOCP 9 exhibits reversible single-crystal-to-single-crystal (SCSC) structural transformation accompanying crystal contraction/expansion upon dehydration/rehydration. Further, when the powdered samples of MOCP 9 were immersed in the aqueous solutions of M(NO3)2 (M = Cu, Co, Ni), cation-exchange induced structural transformation has occurred in the cases of copper and nickel.

並列關鍵字

Coordination Polymer ； Self-Assembly ； Metalloligand

參考文獻

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