开放骨架亚磷酸锰(NH4)2Mn3(HPO3)4和Mn(HPO3)的离子热合成与表征

doi:10.7503/cjcu20140529

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (9): 1859.doi: 10.7503/cjcu20140529

• 研究论文: 无机化学 • 上一篇下一篇

开放骨架亚磷酸锰(NH₄)₂Mn₃(HPO₃)₄和Mn(HPO₃)的离子热合成与表征

何永科, 颜岩, 杨芬, 吴俊标, 宋晓伟()

吉林大学化学学院, 无机合成与制备化学国家重点实验室, 长春 130012

收稿日期:2014-06-11 出版日期:2014-09-10 发布日期:2014-07-28
作者简介:联系人简介: 宋晓伟, 女, 博士, 讲师, 主要从事无机合成化学研究. E-mail: xiaoweisong@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 21001050)和国家“九七三”计划项目(批准号: 2011CB808703)资助

Ionothermal Syntheses and Characterization of Open-framework Manganese Phosphites (NH₄)₂Mn₃(HPO₃)₄ and Mn(HPO₃)^†

HE Yongke, YAN Yan, YANG Fen, WU Junbiao, SONG Xiaowei^*()

State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry,Jilin University, Changchun 130012, China

Received:2014-06-11 Online:2014-09-10 Published:2014-07-28
Contact: SONG Xiaowei E-mail:xiaoweisong@jlu.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(No.21001050) and the National Basic Research Program of China(No.2011CB808703)

摘要/Abstract

摘要：

采用离子热法, 在保持其它合成因素相同的条件下, 仅改变离子液体种类, 合成了2例不同结构的开放骨架亚磷酸锰化合物(NH₄)₂Mn₃(HPO₃)₄(1)和Mn(HPO₃)(2), 并对其单晶结构进行了解析. 化合物1是由MnO₆八面体和亚磷酸根构筑成的二维层状结构化合物, 其中铵根离子填充在层间平衡骨架电荷; 化合物2是由MnO₆八面体和亚磷酸根通过共享顶点氧原子连接构筑而成的致密的三维开放骨架. 通过扫描电子显微镜(SEM)、 X射线单晶结构解析、 X射线粉末衍射(XRD)和元素分析(ICP-AES及CHN)对化合物进行了详细表征. 化合物1的磁学性质研究结果表明其结构中的的Mn²⁺间存在较强的反铁磁相互作用.

关键词: 亚磷酸锰, 离子热合成, 晶体结构, 磁性

Abstract:

Two open-framework manganese phosphites, (NH₄)₂Mn₃(HPO₃)₄(1) and Mn(HPO₃)(2), were synthesized under ionothermal conditions and characterized by single crystal X-ray diffraction. The two compounds were synthesized under the same conditions, but the structures were different with the use of diffe-rent ionic liquids. The framework structure of compound 1 is built up from MnO₆ octahedra and phosphite groups, giving rise to a two-dimensional framework with N $H 4 +$ cations filling between the layers; the structure of compound 2 consists of a 3D condensed framework of edge-sharing MnO₆ octahedra linking to [HPO₃] units via oxygens. The compounds were further characterized by scanning electron microscopy(SEM), powder X-ray diffraction(PXRD) and inductively coupled plasma(ICP), and the magnetic measurements results reveal that strong antiferromagnetic interaction exists in compound 1.

Key words: Manganese phosphite, Ionothermal synthesis, Crystal structure, Magnetic property

中图分类号:

O614.7

TrendMD:

何永科, 颜岩, 杨芬, 吴俊标, 宋晓伟. 开放骨架亚磷酸锰(NH₄)₂Mn₃(HPO₃)₄和Mn(HPO₃)的离子热合成与表征. 高等学校化学学报, 2014, 35(9): 1859.

HE Yongke, YAN Yan, YANG Fen, WU Junbiao, SONG Xiaowei. Ionothermal Syntheses and Characterization of Open-framework Manganese Phosphites (NH₄)₂Mn₃(HPO₃)₄ and Mn(HPO₃)^†. Chem. J. Chinese Universities, 2014, 35(9): 1859.

图/表 6

Fig.1 SEM images of compounds 1(A) and 2(B)

Table 1 Crystallographic data for compound 1

Empirical formula	H₁₂Mn₃N₂O₁₂P₄	Z	3
M_r	520.81	D_c/(g·cm^-3)	2.673
T/K	296(2)	μ/mm^-1	3.509
λ/nm	0.071073	F(000)	741
Crystal system	Trigonal	θ range/(°)	1.65—28.37
Space group	R $3 ˉ$ m	Goodness-of-fit on F²	1.021
a/nm	0.54415(3)	Limiting indices	-7≤h≤5, -7≤k≤7, -39≤l≤49
b/nm	0.54415(3)	Reflections collected/unique	2364/358
c/nm	3.7114(4)	Completeness to 28.37°	100.0%
α/(°)	90	Data/restraints/parameters	358/6/31
β/(°)	90	R₁, wR₂[I>2σ(I)]	R₁=0.0326, wR₂=0.0883
γ/(°)	120	R₁, wR₂(all data)	R₁=0.0337, wR₂=0.0889
V/nm³	0.95171(13)

Table 1 Crystallographic data for compound 1

Empirical formula	H₁₂Mn₃N₂O₁₂P₄	Z	3
M_r	520.81	D_c/(g·cm^-3)	2.673
T/K	296(2)	μ/mm^-1	3.509
λ/nm	0.071073	F(000)	741
Crystal system	Trigonal	θ range/(°)	1.65—28.37
Space group	R $3 ˉ$ m	Goodness-of-fit on F²	1.021
a/nm	0.54415(3)	Limiting indices	-7≤h≤5, -7≤k≤7, -39≤l≤49
b/nm	0.54415(3)	Reflections collected/unique	2364/358
c/nm	3.7114(4)	Completeness to 28.37°	100.0%
α/(°)	90	Data/restraints/parameters	358/6/31
β/(°)	90	R₁, wR₂[I>2σ(I)]	R₁=0.0326, wR₂=0.0883
γ/(°)	120	R₁, wR₂(all data)	R₁=0.0337, wR₂=0.0889
V/nm³	0.95171(13)

Fig.2 Experimental(a) and simulated(b) XRD patterns of compounds 1(A) and 2(B)

Fig.3 Thermal ellipsoids given at 50% probability

Fig.4 Views of Mn3 cluster formed by MnO6 octahedra(A), Mn3 cluster linking to six adjacent Mn3 clusters by [HPO3] units along the [001] direction(B), the layer consisted of MnO6 and [HPO3] along the [001] direction(C) and NH4+ ions residing between the layers along the [010] direction(D)

Fig.5 Plots of χmT vs. T(A) and 1/χm vs. T(B) for compound 1 (B) Gray solid line represents Curie-Weiss curve fitting in 300—100 K.

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开放骨架亚磷酸锰(NH₄)₂Mn₃(HPO₃)₄和Mn(HPO₃)的离子热合成与表征

Ionothermal Syntheses and Characterization of Open-framework Manganese Phosphites (NH₄)₂Mn₃(HPO₃)₄ and Mn(HPO₃)^†

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