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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >New metal-organic frameworks based on 2,5-thiophenedicarboxylate and pyridine- or imidazole-based spacers: Syntheses, topological structures, and properties
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New metal-organic frameworks based on 2,5-thiophenedicarboxylate and pyridine- or imidazole-based spacers: Syntheses, topological structures, and properties

机译：基于2,5-噻吩二甲酸和吡啶或咪唑基间隔基的新型金属有机骨架：合成，拓扑结构和性质

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摘要

Solvothermal reactions of 2,5-thiophenedicarboxylate (H2tdc) and N-auxiliary ligands in the presence of cobalt(ii), zinc(ii) and cadmium(ii) salts have given rise to seven new metal-organic frameworks, namely, [Co_2(tdc)_2(bpp)_2(H_2O)·(H_2O)]n (bpp = 1,3-bis(4-pyridyl)propane) (1), [Cd(tdc)(bpp)(H_2O)·(H_2O)_2]_n (2), [Zn_2(tdc)_2(bbi)_2·(H_2O)_2]_n (bbi = 1,1′-(1,4-butanediyl) bis(imidazole)) (3), [Co_4(tdc)_3(bimb)_4(H_2O)_5·(tdc)·(DMF)·(H_2O)_2]_n (bimb = 4,4′-bis(1-imidazolyl) biphenyl) (4), [Zn_4(O)(tdc)_3(bimb)_4· (H_2O)_5.25·(CH_3OH)]_n (5), [Cd_4(tdc)_4(bimb)_6·(H_2O)_2·(CH_3OH)_2·(DMF)_4] (6) and [Co_2(tdc)_2(tib)_2·(H_2tdc)·(DMF)_2] (tib = 1,3,5-tris(1-imidazolyl) benzene) (7), which exhibit structural diversity. Compounds 1-3 display 3D 2-fold interpenetrating 8-connected tsi net, 2D 4-connected sql net, and 3D 5-fold interpenetrating 4-connected dia net, respectively; while compound 4 features an extremely rare 3D 7-connected hxg-d cationic net and compound 5 adopts a 3D trinodal (4,4,6)-connected net with a new topology structure. For compounds 6 and 7, the topology in the structures were determined as 3D 3-fold interpenetrating 5-connected bnn net and 3D 2-fold interpenetrating binodal (3,5)-connected net, respectively. In the solid state, complexes 1, 4 and 5 exhibit nonlinear optical properties, and complex 5 has also been evaluated as a promising visible-light-driven photocatalyst for degradation of organic pollutants. The magnetic investigation of complexes 1 and 4 shows that there exists spin-canted antiferromagnetism for 1, whereas strong antiferromagnetic interaction and/or the depopulation of the higher energy Kramers doublets of the Co(ii) centers are dominant in 4.
机译：2,5-噻吩二甲酸（H2tdc）和N-辅助配体在钴（ii），锌（ii）和镉（ii）盐存在下的溶剂热反应产生了七个新的金属有机骨架，即[Co_2 （tdc）_2（bpp）_2（H_2O）·（H_2O）] n（bpp = 1,3-双（4-吡啶基）丙烷）（1），[Cd（tdc）（bpp）（H_2O）·（H_2O ）_2] _n（2），[Zn_2（tdc）_2（bbi）_2·（H_2O）_2] _n（bbi = 1,1'-（1,4-丁二基）双（咪唑））（3），[ Co_4（tdc）_3（bimb）_4（H_2O）_5·（tdc）·（DMF）·（H_2O）_2] _n（bimb = 4,4'-bis（1-咪唑基）联苯）（4），[Zn_4 （O）（tdc）_3（bimb）_4·（H_2O）_5.25·（CH_3OH）] _ n（5），[Cd_4（tdc）_4（bimb）_6·（H_2O）_2·（CH_3OH）_2·（ DMF）_4]（6）和[Co_2（tdc）_2（tib）_2·（H_2tdc）·（DMF）_2]（tib = 1,3,5-三（1-咪唑基）苯）（7），表现出结构多样性。化合物1-3分别显示3D 2倍互穿8联tsi网络，2D 4连sql网络和3D 5互穿4联dia网络。而化合物4具有极为罕见的3D 7连接的hxg-d阳离子网，化合物5采用3D三节点（4,4,6）连接的网，具有新的拓扑结构。对于化合物6和7，结构中的拓扑分别确定为3D 3倍互穿的5连接的bnn网和3D 2倍互穿的二面体（3,5）连接的网。在固态下，配合物1、4和5表现出非线性光学性质，并且配合物5也被评估为一种有前途的可见光驱动的光催化剂，可降解有机污染物。配合物1和4的磁性研究表明，存在针对1的自旋倾斜反铁磁性，而强的反铁磁性相互作用和/或Co（ii）中心的高能Kramers双峰的减少在4中占主导地位。

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