溶剂对镍(Ⅱ)金属有机骨架结构的影响

doi:10.7503/cjcu20160289

摘要/Abstract

摘要：

通过乙酸镍和4-咪唑-1-基-苯甲酸(HL)在不同溶剂热条件下合成了3个新型金属有机骨架化合物[Ni(L)₂]_n·DMF(1), Ni(H₂O)₂(L)₂(2)和Ni(L)₂(CH₃OH)₂(3). 化合物1是用N,N-二甲基甲酰胺(DMF)作为溶剂合成的具有菱形孔道的三维骨架化合物; 化合物2是在DMF/H₂O(体积比4:1)中合成的水作为终端配体参与配位的二维层状化合物, 并通过层与层之间的氢键作用构筑形成了三维超分子结构; 当溶剂为甲醇时, 得到了二维层状化合物3, 且甲醇作为终端配体参与配位. 磁学和电化学性质研究结果表明, 化合物1~3中相邻镍离子之间存在反铁磁相互作用; 在一定的电势范围内出现一对明显的Ni(Ⅱ)/Ni(Ⅲ)氧化还原峰, 表明化合物1~3是潜在的磁性材料或电催化剂材料.

关键词: 金属有机骨架, 磁性, 循环伏安法, 溶剂效应

Abstract:

Solvent is an important influence factor in the self-assembly process of metal-organic framworks. In this article, using the semi-rigid 4-imidazol-1-yl-benzoic acid organic ligand(HL) and Ni(OAc)₂·4H₂O, three novel metal organic frameworks, [Ni(L)₂]_n·DMF(1), Ni(H₂O)₂(L)₂(2) and Ni(OCH₃)₂(HL)₂(3), were synthesized in different solvents. When the solvent was N,N-dimethyl formamide, compound 1 was synthesized, showing a 3D framework with one dimensional diamond channels. Using DMF/H₂O as the solvent, compound 2 was prepared, it exhibits a 2D layer structure with water molecules as terminal ligands, the adjacent layers are linked through hydrogen bonding interactions to form a 3D supramolecular structure. Compound 3 was synthesized in CH₃OH, showing a 2D layer structure. Compounds 1—3 display antiferromagnetic property and exhibit a couple of obvious redox peaks in a certain range of potential, respectively.

Key words: Metal-organic framework, Magnetism, Cyclic voltammetry, Solvent effect

中图分类号:

O614

TrendMD:

高丽娟, 王莉, 王圣燕, 井淑波. 溶剂对镍(Ⅱ)金属有机骨架结构的影响. 高等学校化学学报, 2016, 37(9): 1589.

GAO Lijuan, WANG Li, WANG Shengyan, JING Shubo. Influence of Solvent on Structure of Ni(Ⅱ) Metal-organic Frameworks^†. Chem. J. Chinese Universities, 2016, 37(9): 1589.

图/表 7

Table 1 Crystal data and structure refinement for compounds 1—3

Compound	1	2	3
CCDC No.	1472035	1472036	1472037
Empirical formula	C₂₃H₂₁N₅O₅Ni	C₂₀H₁₈N₄O₆Ni	C₂₂H₂₂N₄O₆Ni
Formula weight	505.69	468.69	497.13
Crystal system	Orthorhombic	Monoclinic	Monoclinic
Space group	Pnna	P2₁/c	P2₁/c
a/nm	1.20404(9)	0.59980(5)	0.78049(16)
b/nm	1.08946(7)	0.74515(6)	1.3323(3)
c/nm	1.74538(12)	2.2385(2)	1.0684(2)
α/(°)	90	90	90
β/(°)	90	100.782(5)	94.03(3)
γ/(°)	90	90	90
Volume/nm³	2.2895(3)	0.98281(14)	1.1082(4)
Z, D_c/(Mg·m^-3)	4, 1.355	2, 1.571	1, 1.490
F(000)	928	484	516
θ range/(°)	2.05—25.10	1.85—25.03	2.45—25.05
Goodness-of-fit on F²	1.051	1.065	1.080
R₁, wR₂[I>2σ(I)]^*	R₁=0.0736, wR₂=0.1523	R₁=0.0431, wR₂=0.1248	R₁=0.0319, wR₂=0.0727
R₁, wR₂(all data)^*	R₁=0.0915, wR₂=0.1598	R₁=0.0497, wR₂=0.1308	R₁=0.0494, wR₂=0.0809
Largest difference in peak and	639 and -617	745 and -603	226 and -351
hole/(e·nm^-3)

Fig.1 Coordination environment of Ni(Ⅱ) in compound 1(A), coordination mode of ligand(B), stick view of 3D structure of compound 1 along the y-axis, showing the diamond windows in the xz plane(C) and topology of the four-fold interpenetration in compound 1(D) The hydrogen atoms are omitted for clarity.

Fig.2 Coordination environment of Ni(Ⅱ) in compound 2(A), coordination mode of ligand(B), view of the left- and right- handed helical chains(C), view of the 2D layer structure constructed by the 1D helical chain(D), view of the topological structure of the 2D layer(E) and view of the 3D supramolecular structure constructed by the 2D layer via hydrogen-bond interactions(F) The hydrogen atoms are omitted for clarity.

Fig.3 Coordination environment of Ni(Ⅱ) in compound 3(A), coordination mode of ligand(B), view of the left- and right-handed helical chains(C) and view of the 2D layer structure constructed by the 1D helical chain(D)

Fig.4 View of the topological structure of the 2D layer of compound 3

Fig.5 Temperature dependence of χmT and 1/χm for compound 1 The solid line shows the fitting result.

Fig.6 Cyclic voltammograms of compounds 1(A), 2(B) and 3(C)

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