Co(Ⅱ)-Zn(Ⅱ)掺杂配位聚合物的合成及物理性能

doi:10.7503/cjcu20190395

摘要/Abstract

摘要：

采用均苯三甲酸配体、硝酸锌与硝酸钴反应, 一步合成了钴掺杂的锌配位聚合物Zn_1-_xCo_x(BTC)·(OH)(H₂O)₃(NMP)(DMF)(H₂O)_1.5(H₃BTC为1,3,5-均苯三酸, NMP为1-甲基-2-吡咯烷酮, DMF为N,N'-二甲基甲酰胺, x=0~0.8). 该化合物结构经X射线单晶衍射确定, 属于立方晶系, 空间群P2₁3, 晶胞参数a=1.43863(20) nm. 利用元素分析、能量散色光谱(EDS)、 UV-Vis光谱、 X射线粉末衍射(XRD)、热重分析(TGA)、氮气吸附和磁性分析等表征手段对样品的物理性质进行了表征. 氮气吸附实验结果表明, 该配位聚合物具有良好的微孔吸附特性, Langmiur比面积为832 m ²/g, 孔径为0.84 nm; 元素分析结果表明, 钴/锌摩尔比为1∶1时, 在37~300 K温度范围内其磁性表现为反铁磁性, 并满足Curie-Weiss定律.

关键词: 金属有机骨架材料, 配位聚合物, 异核配合物, 磁性

Abstract:

Coordination polymer ZnCo(BTC)(OH)(H₂O)₃(NMP)(DMF)(H₂O)_1.5 was synthesized by slowly diffusing a balanced amount of organic amine into a solution of 1,3,5-benzenetricarboxylate(H₃BTC), zinc nitrate and cobalt nitrate. X-ray single crystal diffraction shows that the compound crystallizes in cubic, space group P2₁3, and its cell parameter is 1.43863(20) nm. Its physical properties were characterized by elemental analysis(EA), energy-dispersive X-ray spectroscopy(EDS), X-ray powder diffraction(XRD), N₂ sorption and variable-temperature magnetic susceptibility. The gas sorption shows this compound holds Ⅰ-isotherm characteristic of micropore, which is 0.84 nm of pore size and 832 m ²/g of langmiur surface area. The magnetic results show that it exhibits antiferromagnetism in the temperature range of 37—300 K.

Key words: Metal-organic frameworks, Coordination polymer, Heterometal complex, Magnetic property

中图分类号:

O611.4

TrendMD:

石宝珍,李杉,王佃鹏,周云志,孙锦玉. Co(Ⅱ)-Zn(Ⅱ)掺杂配位聚合物的合成及物理性能. 高等学校化学学报, 2019, 40(12): 2443.

Baozhen SHI,Shan LI,Dianpeng WANG,Yunzhi ZHOU,Jinyu SUN. Synthesis and Physical Properties of Cobalt-Zinc Hybrid Porous Metal-organic Frameworks ^†. Chem. J. Chinese Universities, 2019, 40(12): 2443.

图/表 7

参考文献 31

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Empirical formula	C₉H₁₀O₁₀CoZn	θ range/(°)	2.00—28.62
Formula mass	402.47	Limiting indices	-18≤h≤17
Temperature/K	296(2)		-17≤k≤19
λ/nm	0.071073		-19≤l≤13
Crystal system	Cubic	Collected/unique reflns	20650/2467(R_int=0.0815)
Space group	P2₁3	Completeness to θ	97.5
a/nm	1.43863(20)	Refinement method on F²	Full-matrix least-squares
V/nm³	2.9775(7)	Data/restraints/parameters	2467/1/69
Z	4	Goodness-of-fit on F²	0.924
D_calcd./(Mg·m^-3)	0.898	Final R indices[I>2σ(I)]	R₁=0.0705, wR₂=0.1802
μ/mm^-1	1.384	R indices(all data)	R₁=0.1192, wR₂=0.1998
F(000)	804	Δρ_max, Δρ_min/(e·nm^-3)	538, -314

Empirical formula	C₉H₁₀O₁₀CoZn	θ range/(°)	2.00—28.62
Formula mass	402.47	Limiting indices	-18≤h≤17
Temperature/K	296(2)		-17≤k≤19
λ/nm	0.071073		-19≤l≤13
Crystal system	Cubic	Collected/unique reflns	20650/2467(R_int=0.0815)
Space group	P2₁3	Completeness to θ	97.5
a/nm	1.43863(20)	Refinement method on F²	Full-matrix least-squares
V/nm³	2.9775(7)	Data/restraints/parameters	2467/1/69
Z	4	Goodness-of-fit on F²	0.924
D_calcd./(Mg·m^-3)	0.898	Final R indices[I>2σ(I)]	R₁=0.0705, wR₂=0.1802
μ/mm^-1	1.384	R indices(all data)	R₁=0.1192, wR₂=0.1998
F(000)	804	Δρ_max, Δρ_min/(e·nm^-3)	538, -314