由羧酸和含氮杂环配体构筑从核到双链结构的金属有机骨架
Frameworks of Metal Dicarboxylate Complexes: from Nuclear Structures to Double Chains Based on N-containing Ligands
作者单位E-mail
顾晓敏 江苏大学化学化工学院, 镇江 212013  
王蕾 江苏大学化学化工学院, 镇江 212013  
单月霞 江苏大学化学化工学院, 镇江 212013  
张文莉 江苏大学化学化工学院, 镇江 212013 zhangwl@ujs.edu.cn 
陈钦 江苏大学化学化工学院, 镇江 212013  
倪良 江苏大学化学化工学院, 镇江 212013  
姚加 浙江大学化学系, 杭州 310027  
摘要: 通过水热法合成了3个配合物{[Mn(4, 4'-oba)(Medpq)]Medpq}n (1), [Mn2(4, 4'-oba)2(MOPIP)4]·2H2O (2)和[Cd(ox)(MOPIP)2]·2H2O (3)(4, 4'-H2oba=4, 4'-二苯醚二甲酸, H2ox=草酸, Medpq=2-甲基吡嗪[3, 2-f:2, 3'-h]喹喔啉, MOPIP=2-(-甲氧基)-氢-咪唑[4, 5-f][1, 10]菲咯啉), 并通过X-射线单晶衍射分析得出它们的晶体结构。配合物1表现为一个一维的双链结构。 配合物2和3分别为双核和单核的零维离散结构, 在π-π堆积和氢键的作用下, 进一步形成了三维网络状结构。结构分析结果表明氮杂环和二羧酸配体对配合物的结构有很大影响。此外, 在室温下对配合物23进行了荧光性质分析。
关键词: 荧光性质  结构多样性  相互作用  自然键轨道分析
基金项目: 江苏大学高级人才启动基金项目(No.14JDG053),江苏省博士后科学基金(No.1401176C)资助项目。
Abstract: Three complexes have been obtained by the reaction of metal (Mn(Ⅱ), Cd(Ⅱ)), 5,6-substituted 1,10-phen derivatives with two carboxylic acids, 4,4'-oxybis(benzoic acid)(4,4'-H2oba) and oxalic acid (H2ox). The crystal structures of the resulting complexes, namely {[Mn(4,4'-oba)(Medpq)]Medpq}n (1), [Mn2(4,4'-oba)2(MOPIP)4]·2H2O (2), and [Cd(ox)(MOPIP)2]·2H2O (3) (Medpq=2-methyldipyrido-[3,2-f:2,3'-h]quinoxaline, MOPIP=2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline]), have been elucidated using their single-crystal X-ray diffraction analysis. Diverse structures are observed for these complexes. Compound 1 contains double chains, which are further stacked via hydrogen bonding interactions to form layers. Compound 2 features dinuclear structures, which are connected by strong ππ and hydrogen bonding interactions to result in layer structures. Compound 3 contains mononuclear structures and extended to chain and layer structures by ππ and hydrogen bonding interactions. The differences among these structures indicate that the size of the rigid chelating ligands and the flexibility of carboxylate have important effects on the structures of their complexes. The fluorescent properties of 2 and 3 were studied in the solid state at room temperature.
Keywords: fluorescent property  structural diversity  interactions  NBO analysis
投稿时间:2014-09-01 修订日期:2015-01-06
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顾晓敏,王蕾,单月霞,张文莉,陈钦,倪良,姚加.由羧酸和含氮杂环配体构筑从核到双链结构的金属有机骨架[J].无机化学学报,2015,31(3):555-564.
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