Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH2)(3)][M-II(HCOO)(3)] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH2)(3)=Guanidinium)

doi:10.1002/chem.200901605

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	Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH2)(3)][M-II(HCOO)(3)] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH2)(3)=Guanidinium)
	Hu, Ke-Li 1; Kurmoo, Mohamedally 2; Wang, Zheming 1; Gao, Song 1
刊名	CHEMISTRY-A EUROPEAN JOURNAL
	2009
卷号	15 期号:44 页码:12050-12064
关键词	Structure Elucidation Guanidinium Magnetic Properties Metal Formates Metal-organic Perovskites
ISSN号	0947-6539
DOI	10.1002/chem.200901605
英文摘要	We report the synthesis, crystal structures, and spectral, thermal, and magnetic properties of a family of metal-organic perovskite ABX(3), [C(NH2)(3)][M-II(HCOO)(3)], in which A=C-(NH2)(3) is guanidinium, B=M is a divalent metal ion (Mn, Fe, Co, Ni, Cu, or Zn), and X is the formate HCOO-. The compounds could be synthesized by either diffusion or hydrothermal methods from water or water-rich solutions depending on the metal. The five members (Mn, Fe, Co, Ni, and Zn) are isostructural and crystallize in the orthorhombic space group Pnna, while the Cu member in Pna2(1). In the perovskite structures, the octahedrally coordinated metal ions are connected by the anti-anti formate bridges, thus forming the anionic NaCl-type [M(HCOO)(3)](-) frameworks, with the guanidinium in the nearly cubic cavities of the frameworks. The Jahn-Teller effect of Cu2+ results in a distorted anionic Cu-formate framework that can be regarded as Cu-formate chains through short basal Cu-O bonds linked by the long axial Cu-O bonds. These materials show higher thermal stability than other metal-organic perovskite series of [AmineH][M(HCOO)(3)] templated by the organic monoammonium cations (AmineH(+)) as a result of the stronger hydrogen bonding between guanidinium and the formate of the framework. A magnetic study revealed that the five magnetic members (except Zn) display spin-canted antiferromagnetism, with a Neel temperature of 8.8 (Mn), 10.0 (Fe), 14.2 (Co), 34.2 (Ni), and 4.6 K (Cu). In addition to the general spin-canted antiferromagnetism, the Fe compound shows two isothermal transformations (a spin-flop and a spin-flip to the paramagnetic phase) within 50 kOe. The Co member possesses quite a large canting angle. The Cu member is a magnetic system with low dimensional character and shows slow magnetic relaxation that probably results from the domain dynamics.
语种	英语
出版者	WILEY-BLACKWELL
WOS记录号	WOS:000272109100031
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/67597]
专题	中国科学院化学研究所
通讯作者	Wang, Zheming
作者单位	1.Peking Univ, Beijing Natl Lab Mol Sci, State Key Lab Rare Earth Mat Chem & Applicat, Coll Chem & Mol Engn, Beijing 100871, Peoples R China 2.Univ Strasbourg, Chim Coordinat Organ Lab, CNRS, UMR7140,Inst Le Bel, F-67000 Strasbourg 01, France
推荐引用方式 GB/T 7714	Hu, Ke-Li,Kurmoo, Mohamedally,Wang, Zheming,et al. Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH2)(3)][M-II(HCOO)(3)] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH2)(3)=Guanidinium)[J]. CHEMISTRY-A EUROPEAN JOURNAL,2009,15(44):12050-12064.
APA	Hu, Ke-Li,Kurmoo, Mohamedally,Wang, Zheming,&Gao, Song.(2009).Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH2)(3)][M-II(HCOO)(3)] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH2)(3)=Guanidinium).CHEMISTRY-A EUROPEAN JOURNAL,15(44),12050-12064.
MLA	Hu, Ke-Li,et al."Metal-Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [C(NH2)(3)][M-II(HCOO)(3)] (M=Mn, Fe, Co, Ni, Cu, and Zn; C(NH2)(3)=Guanidinium)".CHEMISTRY-A EUROPEAN JOURNAL 15.44(2009):12050-12064.