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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-Li1; Kurmoo, Mohamedally2; Wang, Zheming1; Gao, Song1
2009
Source PublicationCHEMISTRY-A EUROPEAN JOURNAL
ISSN0947-6539
Volume15Issue:44Pages:12050-12064
AbstractWe 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.
KeywordStructure Elucidation Guanidinium Magnetic Properties Metal Formates Metal-organic Perovskites
DOI10.1002/chem.200901605
Indexed BySCI
Language英语
WOS IDWOS:000272109100031
PublisherWILEY-BLACKWELL
Citation statistics
Cited Times:161[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/67598
Collection中国科学院化学研究所
Corresponding AuthorWang, Zheming
Affiliation1.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
Recommended Citation
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.
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