Perovskite-Like Polar Lanthanide Formate Frameworks of   [NH2NH3][Ln(HCOO)(4)] (Ln = Tb-Lu and Y): Synthesis, Structures,   Magnetism, and Anisotropic Thermal Expansion

doi:10.1021/acs.inorgchem.6b00952

CORC > 北京大学 > 化学与分子工程学院

	Perovskite-Like Polar Lanthanide Formate Frameworks of [NH2NH3][Ln(HCOO)(4)] (Ln = Tb-Lu and Y): Synthesis, Structures, Magnetism, and Anisotropic Thermal Expansion
	Zhao, Tian-Meng ; Chen, Sa ; Shang, Ran ; Wang, Bing-Wu ; Wang, Zhe-Ming ; Gao, Song
刊名	INORGANIC CHEMISTRY
	2016
关键词	METAL-ORGANIC FRAMEWORKS PROMINENT DIELECTRIC ANOMALIES NEGATIVE LINEAR COMPRESSIBILITY WEAK FERROMAGNETISM PHASE-TRANSITION MECHANICAL-PROPERTIES COPPER-FORMATE CO ZN NI
DOI	10.1021/acs.inorgchem.6b00952
英文摘要	A series of isostructural hydrazinium lanthanide (Ln) formate framework compounds of [NH2NH3] [Ln(HCOO)(4)] for Ln(3+) ions from Tb3+ to Lu3+ and Y3+ have been successfully prepared by utilizing NH2NH3+. The compounds crystallize in orthorhombic polar space group Pca2(1), with cell parameters at 180 K of a = 18.2526(7)-18.1048(5) angstrom, b = 6.5815(2)-6.5261(2) angstrom, c = 7.6362(3)-7.5044(2) angstrom, and V = 917.33(6)-886.67(4) angstrom(3), showing the effect of lanthanide contraction. The compounds possess polar perovskite-like structures incorporating the hydrazinium cations in the cavities of the NaCl-like framework, in which the Ln(3+) ions in a bicapped trigonal prism are connected by anti-anti and syn-anti formate groups. The N-H center dot center dot center dot O-formate hydrogen-bonding interactions are between the hydrazinium cations and the anionic framework. One anti-anti formate group is frustrated by the competitive N-H center dot center dot center dot O-formate hydrogen-bonding interactions. It thus twists or flips upon warming, resulting in large anisotropic thermal expansion and negative thermal expansion below 180 K. A comparison with the transition metal and magnesium analogues revealed that the structural compactness, tighter binding of the hydrazinium cation by the framework, and symmetrically better match between the framework and ammonium cation for Ln compounds could inhibit the occurrence of phase transition in the series. The IR spectroscopic, thermal, and magnetic properties are investigated.; NSFC [21171010, 91422302, 21321001, 21290170, 21290171]; National Basic Research Program of China [2013CB933401]; SCI(E); PubMed; ARTICLE; zmw@pku.edu.cn; gaosong@pku.edu.cn; 20; 10075-10082; 55
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/493566]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Zhao, Tian-Meng,Chen, Sa,Shang, Ran,et al. Perovskite-Like Polar Lanthanide Formate Frameworks of [NH2NH3][Ln(HCOO)(4)] (Ln = Tb-Lu and Y): Synthesis, Structures, Magnetism, and Anisotropic Thermal Expansion[J]. INORGANIC CHEMISTRY,2016.
APA	Zhao, Tian-Meng,Chen, Sa,Shang, Ran,Wang, Bing-Wu,Wang, Zhe-Ming,&Gao, Song.(2016).Perovskite-Like Polar Lanthanide Formate Frameworks of [NH2NH3][Ln(HCOO)(4)] (Ln = Tb-Lu and Y): Synthesis, Structures, Magnetism, and Anisotropic Thermal Expansion.INORGANIC CHEMISTRY.
MLA	Zhao, Tian-Meng,et al."Perovskite-Like Polar Lanthanide Formate Frameworks of [NH2NH3][Ln(HCOO)(4)] (Ln = Tb-Lu and Y): Synthesis, Structures, Magnetism, and Anisotropic Thermal Expansion".INORGANIC CHEMISTRY (2016).