并噻吩和三噻吩连接的锰金属有机骨架的合成、结构和磁性。

Synthesis, structure, and magnetic properties of bithiophene- and terthiophene-linked manganese metal-organic frameworks.

机构信息

Department of Chemistry, University of British Columbia, Vancouver, British Columbia, V6T 1Z1 Canada.

出版信息

Inorg Chem. 2013 Sep 3;52(17):10021-30. doi: 10.1021/ic401305c. Epub 2013 Aug 12.

Abstract

A series of metal-organic frameworks (MOFs) containing manganese centers and oligothiophene dicarboxylate linkers have been synthesized: [Mn(3PhT2DC)(DMF)0.45(H2O)2.55·1.55DMF]n (1), [Mn6(3HT2DC)6(DMF)3(H2O)5·xDMF·yH2O]n (2), [Mn(T3DC)(H2O)2]n (3), [Mn(T3DC)(H2O)1.5]n (4), and [Mn(Ph2T3DC)(DMF)2]n (5) (H23PhT2DC = 3,3'-diphenyl-2,2-bithiophene-5,5'-dicarboxylic acid; H23HT2DC= 3,3'-dihexyl-2,2'-bithiophene-5,5'-dicarboxylic acid; H2T3DC = 2,2':5',2″-terthiophene-5,5″-dicarboxylic acid; H2Ph2T3DC = 3',4'-diphenyl-2,2':5',2″-terthiophene-5,5″-dicarboxylic acid, DMF = N,N-dimethylformamide). Compound 1 exists as a 2D sheet, 2-4 are 3D frameworks, and 5 is a 1D chain. Compounds 3 and 4 are isomers, and 3-5 are the first examples of crystallographically characterized terthiophene coordination polymers. In the case of 1, 2, and 5, the extended structure is sensitive to β substitution of the oligothiophene linkers. Compounds 1-3 and 5 show antiferromagnetic behavior with typical values of g and J, and 3 exhibits a spin canting transition at 40 K.

摘要

一系列含有锰中心和寡聚噻吩二羧酸连接体的金属-有机骨架（MOFs）已被合成：[Mn(3PhT2DC)(DMF)0.45(H2O)2.55·1.55DMF]n (1)、[Mn6(3HT2DC)6(DMF)3(H2O)5·xDMF·yH2O]n (2)、[Mn(T3DC)(H2O)2]n (3)、[Mn(T3DC)(H2O)1.5]n (4) 和 [Mn(Ph2T3DC)(DMF)2]n (5)（H23PhT2DC = 3,3'-二苯基-2,2'-联噻吩-5,5'-二羧酸；H23HT2DC = 3,3'-二己基-2,2'-联噻吩-5,5'-二羧酸；H2T3DC = 2,2':5',2″-并噻吩-5,5″-二羧酸；H2Ph2T3DC = 3',4'-二苯基-2,2':5',2″-并噻吩-5,5″-二羧酸，DMF = N,N-二甲基甲酰胺）。化合物 1 为二维层状结构，2-4 为三维骨架，5 为一维链状结构。化合物 3 和 4 为异构体，而 3-5 为首次结晶学表征的并噻吩配位聚合物的实例。在 1、2 和 5 的情况下，扩展结构对寡聚噻吩连接体的β取代敏感。化合物 1-3 和 5 表现出反铁磁行为，具有典型的 g 值和 J 值，并且 3 在 40 K 处表现出自旋倾斜转变。