Shi Zhenzhen, Pan Zhaorui, Zhang Chuanlei, Zheng Hegen
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, P. R. China.
Dalton Trans. 2015 Oct 14;44(38):16854-64. doi: 10.1039/c5dt02774h. Epub 2015 Sep 8.
Six new cobalt(ii) metal-organic frameworks, {[Co1.5(TTPA)(BTC)(H2O)]2·13H2O}n (1), [Co(TTPA)(PA)]n (2), {[Co(TTPA)(BDA)0.5(NO3)]·3H2O}n (3), {[Co2(TTPA)3(OBA)2(H2O)3]·2CH3CN·4H2O}n (4), {[Co(TTPA)(AIP)(H2O)]·2H2O}n (5), and {[Co(TTPA)(MIP)(H2O)]·2H2O}n (6), have been prepared by the self-assembly of a tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine (TTPA) ligand with different aromatic carboxylate auxiliary ligands (H3BTC = 1,3,5-benzenetricarboxylic acid, H2PA = phthalic acid, H2BDA = (1,1'-biphenyl)-4,4'-dicarboxylic acid, H2OBA = 4,4'-oxydibenzoic acid, H2AIP = 5-aminoisophthalic acid, H2MIP = 5-methylisophthalic acid) and cobalt salts. Their structures have been characterized by infrared spectroscopy, elemental analysis, single crystal X-ray analysis, and powder X-ray diffraction. Complex 1 is an unusual 4-nodal (3,3,4,8)-connected three-dimensional (3D) new topological net with the point symbol of (4·6·8)4(4(4)·6(7)·8(15)·10(2))(6(2)·8(4)). Complex 2 has a 2-fold interpenetrating 3D dia framework. Complex 3 displays a rare binodal (3,4)-connected 4-fold interpenetrating 3D architecture with a fsc-3,4-C2/c topology with the point symbol of (4·6·8)(4·6(2)·8(3)). Complex 4 shows two distinct two-dimensional (2D) layers with hcb topologies, which are further packed into a 3D structure by O-HO hydrogen bonding interactions. Both complexes 5 and 6 feature similar 2D sheets with sql topologies, which can be further packed into a 3D structure by O-HO hydrogen bonding interactions. Moreover, the thermal stability and UV-visible spectra of these complexes are also discussed in detail. Meanwhile, the variable-temperature magnetic susceptibility measurement of complex 1 reveals antiferromagnetic interactions between Co(ii) ions.
通过三（4-（1H-1,2,4-三唑-1-基）苯基）胺（TTPA）配体与不同的芳香族羧酸盐辅助配体（H3BTC = 1,3,5-苯三甲酸、H2PA = 邻苯二甲酸、H2BDA = （1,1'-联苯）-4,4'-二羧酸、H2OBA = 4,4'-氧二苯甲酸、H2AIP = 5-氨基间苯二甲酸、H2MIP = 5-甲基间苯二甲酸）和钴盐的自组装，制备了六种新型钴（II）金属有机框架，即{[Co1.5(TTPA)(BTC)(H2O)]2·13H2O}n（1）、[Co(TTPA)(PA)]n（2）、{[Co(TTPA)(BDA)0.5(NO3)]·3H2O}n（3）、{[Co2(TTPA)3(OBA)2(H2O)3]·2CH3CN·4H2O}n（4）、{[Co(TTPA)(AIP)(H2O)]·2H2O}n（5）和{[Co(TTPA)(MIP)(H2O)]·2H2O}n（6）。通过红外光谱、元素分析、单晶X射线分析和粉末X射线衍射对它们的结构进行了表征。配合物1是一种不寻常的4节点（3,3,4,8）连接的三维（3D）新拓扑网络，点符号为（4·6·8）4（4(4)·6(7)·8(15)·10(2))(6(2)·8(4))。配合物2具有一个2重互穿的3D dia框架。配合物3展示了一种罕见的双节点（3,4）连接的4重互穿3D结构，具有fsc-3,4-C2/c拓扑结构，点符号为（4·6·8）(4·6(2)·8(3))。配合物4显示出两个具有hcb拓扑结构的不同二维（2D）层，它们通过O-HO氢键相互作用进一步堆积成3D结构。配合物5和6都具有类似的具有sql拓扑结构的2D片层，它们可以通过O-HO氢键相互作用进一步堆积成3D结构。此外，还详细讨论了这些配合物的热稳定性和紫外可见光谱。同时，配合物1的变温磁化率测量揭示了Co（II）离子之间的反铁磁相互作用。
