四氮杂大环镍与[M(dmit)2]2-的离子对配合物[NiL][M(dmit)2]的合成与表征

Syntheses and Characterizations of Bimetal Ion-Pair Complexes [M(dmit)_2]Based on Tetraazamacrocycle Nickel Cation and [M(dmit)_2]^(2-)

以1,3-二硫杂环戊烯-4,5-二硫醇-2-硫酮(dmit)和5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四-1,8-二烯(hmtade)或5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷(hmta)为配体合成了4个双金属的离子对配合物[NiL][M(dmit)2](L=hmtade,M=Ni(1);L=hmta,M=Ni(2);L=hmtade,M=Hg(3);L=hmta,M=Hg(4))。用元素分析、红外光谱、核磁共振氢谱、紫外-可见光谱、热重分析和循环伏安法等对它们进行了表征。研究结果表明,大环配体hmta、hmtade和配体dmit之间形成了N-H…S氢键,配阳离子均为五配位,配阴离子[M(dmit)2]2-的S对配阳离子的Ni(II)进行了配位。离子对配合物的稳定性顺序为:2>1>3>4。

Four bimetal ion-pair complexes, [NiL][M（dmit）2] （L= hmtade, M=Ni（1）; L=hmta, M=Ni （2）; L=hmtade, M --Hg（3）; L =hmta, M =Hg（4）, where hmtade =5,7,7,12,14,14-hexamethyl-l,4,8,11. tetraazacyclotetradeca-4,11 -diene, hmta = 5,5,7,12,12,14-hexamethyl-1,4,8,11 -tetraazacyclotetradecane, dmit = 4,5-dimercapto-1,3-dithiole-2-thione） were synthesized and characterized by elemental analysis, IR, ~H NMR, UV- vis, thermogravimetry and cyclic vohammetry, The results showed that N--H-.. S hydrogen bonds were formed between hmtade/hmta and dmit ligands in the ion-pair complexes. All of the nickel ions of complex cations are five coordination. The S atom of [ M （dmit）2 ] 2- complex anion coordinates to Ni（Ⅱ） ions of tetraazamacrocycle complex cation. The stability sequence of the ion-pair complexes is ： 2 〉 1 〉 3 〉 4.