具有穿插结构的金属钴配合物的合成、 结构及电化学性质

doi:10.7503/cjcu20170650

摘要/Abstract

摘要：

在溶剂热体系中合成了3个中心金属为钴离子的具有穿插结构的金属有机配合物{[CoLB]·H₂O}_n(1), {[Co₂L₂(bimp)_0.5]·3H₂O}_n(2)和{[Co₂L₂B'₂]·2DMF}_n(3) [H₂L=4,4'-三苯胺二甲酸; B=1,3-二(咪唑基)苯, bimp=3,5-二(1-咪唑)吡啶, B'=1,4-双(咪唑基)苯]. 通过单晶及粉末X射线衍射和热重分析对这3个配合物进行了表征. 结果表明, 配合物1~3均结晶于单斜晶系, 其中配合物1属C2/c空间群, 配合物2属P2/n空间群, 配合物3属P2₁空间群; 在配合物1和3中Co²⁺为四配位模式, 而在配合物2中Co²⁺为五配位, 并以双核桨轮形的结构单元[Co₂(CO₂)₄]存在; 配合物1和2均为二重穿插结构的三维超分子网络, 配合物3是一个四重穿插的三维超分子网络. 电化学性质研究结果表明, 配合物1~3是电化学活性物质, 电化学可逆性较好.

关键词: 金属有机骨架, 钴配合物, 穿插结构, 循环伏安法

Abstract:

Using multidenate 4,4'-(phenylazanediyl)dibenzoic acid(H₂L) and 1,3-bis(imidazol-l-yl)benzene(B), 3,5-bis(imidazol-l-yl)pyridine(bimp) or 1,4-bis(imidazol-l-yl)benzene(B') as ligands under solvothermal conditions, three new metal-organic frameworks with interpenetrating structure, {[CoLB]·H₂O}_n(1), {[Co₂L₂(bimp)_0.5]·3H₂O}_n(2) and {[Co₂L₂B'₂]·2DMF}_n(3), were synthesized. The complexes were characterized by single-crystal X-ray diffraction(XRD), thermal analysis and powder X-ray diffraction(PXRD). Complexes 1—3 all crystallize in the monoclinic system, with C2/c(complex 1), P2/n(complex 2) and P2₁(complex 3) space group, respectively. In complexes 1 and 3, Co²⁺ forms a tetracoordinate geometry, whereas it forms a five-coordinated geometric configuration and exists as a dual-core paddle-shaped structural unit [Co₂(CO₂)₄] in complex 2. Complexes 1 and 2 give a 2-fold interpenetrating three-dimensional(3D) supramolecular networks, while complex 3 exhibits a 4-fold interpenetrating 3D framework. The results of electrochemical studies show that complexes 1—3 are electrochemically active substances with good electrochemical reversibility.

Key words: Metal-organic framework(MOF), Cobalt complex, Interpenetrating structure, Cyclic voltammetry

赵长江, 刘欣, 田利, 赵仑. 具有穿插结构的金属钴配合物的合成、结构及电化学性质[J]. 高等学校化学学报, 2018, 39(5): 861-868.

ZHAO Changjiang,LIU Xin,TIAN Li,ZHAO Lun. Synthesis, Structure and Electrochemical Properties of Metal Cobalt Complexes with Interpenetrating Structures^†[J]. Chemical Journal of Chinese Universities, 2018, 39(5): 861-868.

图/表 9

Fig.1 Molecular structures of the ligands

Table 1 Crystal data and structure refinement of complexes 1—3

Complex	1	2	3
CCDC No.	1575252	1575253	1575254
Molecular formula	C₃₂H₂₅CoN₅O₅	C₅₁H₄₇Co₂N₇O₁₃	C₇₀H₆₀Co₂N₁₂O₁₀
F_w	618.51	1083.82	1347.16
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	C2/c	P2/n	P2₁
a/nm	2.7443(10)	1.58338(11)	1.1130(3)
b/nm	1.0762(4)	0.86972(6)	2.1039(5)
c/nm	2.2217(9)	1.75432(12)	2.6929(7)
α/(°)	90.00	90.00	90.00
β/(°)	90.12	94.5160(10)	90.00
γ/(°)	90.00	90.00	90.12
V/nm³	6.562(4)	2.4084(3)	6.306(3)
Z	8	2	4
D_c/(g·cm^-3)	1.252	1.495	1.419
F(000)	2552	1120	2792
GOF on F²	0.916	1.058	0.851
R₁, wR₂[I>2σ(I)]	0.0815, 0.2116	0.0565, 0.1562	0.0744, 0.1334
R₁, wR₂(all data)	0.1462, 0.2308	0.1060, 0.1971	0.2324, 0.1822

Fig.2 Coordination environment of the Co(Ⅱ) ions(A) and views of 2D sheets(B), 3D framework(C), topology network(D) and the two-fold interpenetrating framework(E) of complex 1 The hydrogen atoms are omitted for clarity. Symmetry codes: #1. x-1/2, y+1/2, z; #2. x, -y-1, z+1/2; #3. x+1/2, y-1/2, z; #4. x, -y-1, z-1/2.

Fig.3 Coordination environment of the Co(Ⅱ) ions(A) and views of 2D sheets(B), 3D framework(C), topology of 3D framework(D), two-fold interpenetrating framework(E) and the helical chains(F) of complex 2 The hydrogen atoms are omitted for clarity. Symmetry codes: #1. -x+3/2, y, -z+3/2; #2. -x+3/2, y+1, -z+1/2; #3. x-1/2, -y+2, z-1/2; #4. -x+2, -y+1, -z+1; #5. x+1/2, -y+2, z+1/2; #6. -x+3/2, y-1, -z+1/2; #7. -x+3/2, y, -z+1/2.

Fig.4 Coordination environment of Co(Ⅱ) ions(A) and views of 3D framework(B), topology network of 3D framework(C), four-fold interpenetrating framework(D) and the two different helical chains(E, F) of complex 3 The hydrogen atoms are omitted for clarity. Symmetry codes: #1. -x+5/2, y+1/2, -z+3/2; #2. x-2, y, z; #3. -x+5/2, y-1/2, -z+3/2; #4. x+2, y, z; #5. -x+1/2, y-1/2, -z+1/2; #6. -x+1/2, y+1/2, -z+1/2.

Fig.5 Experimental(a) and simulated(b) PXRD patterns of complex 1(A), complex 2(B) and complex 3(C)

Fig.6 TG curves of complexes 1(a), 2(b) and 3(c)

Fig.7 Cyclic voltammograms of complex 1(A), complex 2(B) and complex 3(C)

Fig.8 Cyclic voltammograms at different sweep speeds(A) and I-v1/2 plots(B) of complex 1(A, A'), complex 2(B, B') and complex 3(C, C') (A)—(C) Scan rate/(mV·s-1): a. 50; b. 70; c. 90; d. 110; e. 130; f. 150; g. 170; h. 200.

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