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Syntheses, structural diversity, magnetic properties and dye absorption of various Co(II) MOFs based on a semi-flexible 4-(3,5-dicarboxylatobenzyloxy)benzoic acid
CrystEngComm ( IF 2.6 ) Pub Date : 2017-10-04 00:00:00 , DOI: 10.1039/c7ce01229b
Xiang-min Meng 1, 2, 3, 4, 5 , Lian-sheng Cui 4, 6, 7, 8 , Xin-ping Wang 1, 2, 3, 4 , Xiao-yin Zhang 3, 5, 9, 10, 11 , Xia Zhang 3, 5, 9, 10, 11 , Shuang-yu Bi 12, 13, 14
Affiliation  

Five novel Co(II) metal–organic frameworks (MOFs) constructed from semi-flexible 4-(3,5-dicarboxylatobenzyloxy)benzoic acid (H3L), namely {[Co1.5(HL)(4,4′-bidpe)2(H2O)]·3H2O}n (1), {[Co3(L)2(4,4′-bibp)32-O)2]·2H2O}n (2), {[Co(HL)(1,3-bitl)]·(1,4-Diox)}n (3), [Co2(HL)2(3,5-bipd)2]n (4), and {[Co(HL)(tib)]·0.5H2O·NMP}n (5) (4,4′-bidpe = 4,4′-bis(imidazolyl)diphenyl ether, 4,4′-bibp = 4,4′-bis(imidazol-1-yl)biphenyl, 1,3-bitl = 1,3-bis(1-imidazoly)toluene, 3,5-bipd = 3,5-bis(1-imidazoly)pyridine, and tib = 1,3,5-tris(1-imidazolyl)benzene), were synthesized under solvothermal conditions and further characterized by elemental analysis, IR spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis and single-crystal X-ray diffraction. Different architectural topologies have been generated by adjusting the N-donor ligands. Single-crystal X-ray diffraction analysis reveals that complex 1 shows a rare 1D → 2D polyrotaxane network. Complex 2 possesses an unprecedented 2-nodal (3,10)-connected 3D framework with a Schläfli symbol of (43)2(46·632·83)(43)2. When the 2-connected points (H3L and 1,3-bitl ligands) are not calculated, complex 3 shows a hcb uninodal 3-connected 2D network with the Schläfli symbol (63), which further constructs a 3D supramolecular structure through O–H⋯O hydrogen bonds; while the 2-connected points are taken into account, complex 3 exhibits an unprecedented 3-nodal (2,2,4)-connected network. Complex 4 presents an unprecedented 2-nodal (3,5)-connected 3D framework with a (4·62)(4·66·83) topology, while complex 5 exhibits another unprecedented 2-nodal (3,5)-connected 2D framework with a (42·67·8)(42·6) Schläfli symbol and shows 2D → 3D supramolecular structure through O–H⋯O hydrogen bonds. Meanwhile, the magnetic properties of complexes 2 and 4 are discussed. Moreover, the dye adsorption and mechanism studies indicate that the pore size, the uncoordinated O atoms in carboxyl groups and the uncoordinated carboxyl groups of the MOFs have significant effects on the dye adsorption capacity.

中文翻译:

基于半柔性4-(3,5-二羧基苯甲基苄氧基)苯甲酸的各种Co(II)MOF的合成,结构多样性,磁性和染料吸收

由半柔性的4-(3,5-二羧基苄基苄氧基)苯甲酸(H 3 L)构成的五个新颖的Co(II)金属-有机骨架(MOF ),即{[Co 1.5(HL)(4,4'-bidpe )2(H 2 O)]·3H 2 ö} ñ1),{[CO 3(L)2(4,4'-BIBP)3(μ 2 -O)2 ]·2H 2 ö} ñ2),{[Co(HL)(1,3-bitl)]·(1,4-Diox)} n3),[Co 2(HL)2(3,5-bipd)2 ] n4)和{[Co(HL)(tib)]·0.5H 2 O·NMP} n5)(4,4'-bidpe = 4,4'-双(咪唑基)二苯醚,4,4 ′-bibp = 4,4'-双(咪唑-1-基)联苯,1,3-位= 1,3-双(1-咪唑基)甲苯,3,5-二苯胺= 3,5-双(1溶剂热条件下合成了1-咪唑基)吡啶和tib = 1,3,5-三(1-咪唑基)苯,并通过元素分析,红外光谱,粉末X射线衍射(PXRD),热重(TG)进行了表征)分析和单晶X射线衍射。通过调节N-供体配体已经产生了不同的结构拓扑。单晶X射线衍射分析表明,配合物1显示出罕见的1D→2D聚轮烷网络。复杂2拥有前所未有的2节点(3,10)连接的3D框架,其Schläfli符号为(4 32(4 6 ·6 32 ·8 3)(4 32。当不计算2个连接点(H 3 L和1,3-bitl配体)时,复合物3会显示带有Schläfli符号(6 3)的hcb单链3连接2D网络,该网络通过以下方式进一步构建了3D超分子结构: O–H⋯O氢键;尽管考虑了2个连接点,但复数3却表现出空前的3节点(2,2,4)连接网络。复杂4提出了一种前所未有的2节点(3,5)连接的3D框架,具有(4·6 2)(4·6 6 ·8 3)拓扑,而复数5展示了另一种前所未有的2节点(3,5)连接的拓扑具有(4 2 ·6 7 ·8)(4 2 ·6)Schläfli符号的2D框架,并通过O–H⋯O氢键显示2D→3D超分子结构。同时,讨论了配合物24的磁性。此外,染料吸附和机理研究表明,MOF的孔径,羧基中未配位的O原子和MOF的未配位羧基对染料的吸附能力有重要影响。
更新日期:2017-11-13
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