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基于二-吡嗪-(2, 3-f: 2′3′-h)-喹喔啉和吡啶-2,5-二羧酸混合配体的两个新奇金属有机超分子骨架的水热合成、晶体结构与光致发光
引用本文:王秀丽,刘国成,林宏艳,陈宝宽,房佳妮,赵海燕. 基于二-吡嗪-(2, 3-f: 2′3′-h)-喹喔啉和吡啶-2,5-二羧酸混合配体的两个新奇金属有机超分子骨架的水热合成、晶体结构与光致发光[J]. 中国化学, 2008, 26(9): 1611-1618. DOI: 10.1002/cjoc.200890291
作者姓名:王秀丽  刘国成  林宏艳  陈宝宽  房佳妮  赵海燕
作者单位:渤海大学化学化工学院,辽宁省应用化学重点实验室,锦州,121000
摘    要:以二-吡嗪-(2, 3-f: 2′3′-h)-喹喔啉(Dpq)和吡啶-2,5-二羧酸(2,5-H2pda)两种混合配体与不同金属硝酸盐为原料,通过水热反应得到了两个新奇的金属有机骨架[Zn2(Dpq)2(2,5-pda)2(H2O)2]·2H2O(1)和[Cd2(Dpq)2(2,5-pda)2]·2H2O(2),并经元素分析、TG、IR、X-射线单晶衍射分析进行了表征。结构分析表明,2,5-pda采取不同的配位方式桥连金属离子分别形成了二聚物1和2D菱形网络2。在化合物1中,相邻的二聚物通过氢键和π-π堆积作用形成扭曲的a-Po超分子结构。在化合物2中,相邻的配位聚合物层通过氢键拓展成扭曲的a-Po超分子骨架,而π-π堆积起到巩固骨架的作用。化合物1和2的结构差异表明了金属离子和配体在配位聚合物自组装过程中对结构的影响。此外固态标题化合物在室温下表现出蓝色的发光性质。

关 键 词:水热合成  晶体结构  分子间作用力  荧光性质
收稿时间:2007-11-10
修稿时间:2008-04-08

Hydrothermal Synthesis,Crystal Structures and Photoluminescence of Two Novel Metal‐organic Supramolecular Frameworks Based on Mixed Ligands of Dipyrazino[2,3‐f:2′,3′‐h]quinoxaline and Pyridine‐2,5‐dicarboxylic Acid
Xiu‐Li WANG,Guo‐Cheng LIU,Hong‐Yan LIN,Bao‐Kuan CHEN,Jia‐Ni FANG,Hai‐Yan ZHAO. Hydrothermal Synthesis,Crystal Structures and Photoluminescence of Two Novel Metal‐organic Supramolecular Frameworks Based on Mixed Ligands of Dipyrazino[2,3‐f:2′,3′‐h]quinoxaline and Pyridine‐2,5‐dicarboxylic Acid[J]. Chinese Journal of Chemistry, 2008, 26(9): 1611-1618. DOI: 10.1002/cjoc.200890291
Authors:Xiu‐Li WANG  Guo‐Cheng LIU  Hong‐Yan LIN  Bao‐Kuan CHEN  Jia‐Ni FANG  Hai‐Yan ZHAO
Affiliation:1. Tel./Fax: 0086‐0416‐3400158;2. Liaoning Key Laboratry of Applied Chemistry, Faculty of Chemistry and Chemical Engineering, Bohai University, Jinzhou, Liaoning 121000, China
Abstract:Two novel metal‐organic frameworks [Zn2(Dpq)2(2,5‐pda)2(H2O)2]·2H2O ( 1 ) (dipyrazino[2,3‐f:2′3′‐h]quinoxaline=Dpq) and [Cd2(Dpq)2(2,5‐pda)2]·2H2O ( 2 ) (pyridine‐2,5‐dicarboxylic acid=2,5‐H2pda) have been obtained from hydrothermal reactions of two different metal(II) nitrates with the same mixed ligands Dpq and 2,5‐H2pda, and structurally characterized by elemental analyses, TG, IR spectroscopy, and single‐crystal X‐ray diffraction analyse. Single‐crystal X‐ray analyses show that the metal ions are bridged by different coordination modes of 2,5‐pda to form a dimer in 1 , 2D rhombic grid in 2 , respectively. In the compound 1 , adjacent dimers are packed through hydrogen bonds and ‐ aromatic stacking interactions to form a distorted α‐Po supramolecular structure. In the compound 2 , adjacent polymer layers are further linked by hydrogen bonds to form a distorted α‐Po 3D supramolecular framework stabilized by ‐ stacking interactions. The different structures of compounds 1 and 2 illustrate the influence of the metal ions and ligands on the self‐assembly of polymeric coordination architectures. In addition, the title compounds exhibit blue emission in the solid state at room temperature.
Keywords:hydrothermal synthesis  crystal structure  intermolecular interaction  fluorescence property
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