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

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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 {[Co_1.5(HL)(4,4′-bidpe)₂(H₂O)]·3H₂O}_n (1), {[Co₃(L)₂(4,4′-bibp)₃(μ₂-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} _ñ（1），{[CO ₃（L）₂（4,4'-BIBP）₃（μ ₂ -O）₂ ]·2H ₂ ö} _ñ（2），{[Co（HL）（1,3-bitl）]·（1,4-Diox）} _n（3），[Co ₂（HL）₂（3,5-bipd）₂ ] _n（4）和{[Co（HL）（tib）]·0.5H ₂ O·NMP} _n（5）（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 ³）²（4 ⁶ ·6 ³² ·8 ³）（4 ³）²。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2和4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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