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首页> 外文期刊>Chemistry: A European journal >Metal–Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [CACHTUNGTRENUNG(NH2)3]ACHTUNGTRENUNG[MIIACHTUNGTRENUNG(HCOO)3] (M=Mn, Fe, Co, Ni, Cu, and Zn; CACHTUNGTRENUNG(NH2)3=Guanidinium)
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Metal–Organic Perovskites: Synthesis, Structures, and Magnetic Properties of [CACHTUNGTRENUNG(NH2)3]ACHTUNGTRENUNG[MIIACHTUNGTRENUNG(HCOO)3] (M=Mn, Fe, Co, Ni, Cu, and Zn; CACHTUNGTRENUNG(NH2)3=Guanidinium)

机译：金属有机钙钛矿：[CACHTUNGTRENUNG（NH2）3] ACHTUNGTRENUNG [MIIACHTUNGTRENUNG（HCOO）3]（M = Mn，Fe，Co，Ni，Cu和Zn; CACHTUNGTRENUNG（NH2）3 =胍盐）

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We report the synthesis, crystal structures, and spectral, thermal,and magnetic properties of a family of metal–organic perovskite ABX3, [CACHTUNGTRENUNG(NH2)3]ACHTUNGTRENUNG MIIACHTUNGTRENUNG(HCOO)3], in which A=CACHTUNGTRENUNG( 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 Pna21. In the perovskite structures, the octahedrally coordinated metal ions are connected by the anti–anti formate bridges, thus forming the anionic NaCl-type [MACHTUNGTRENUNG( 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 CuO bonds linked by the long axial CuO bonds. These materials show higher thermal stability than other metal–organic perovskite series of [AmineH][MACHTUNGTRENUNG(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 Nel 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 spinflip 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.
机译：我们报告了一族金属-有机钙钛矿ABX3 [CACHTUNGTRENUNG（NH2）3] ACHTUNGTRENUNG MIIACHTUNGTRENUNG（HCOO）3]的合成，晶体结构以及光谱，热和磁性能，其中A = CACHTUNGTRENUNG（NH2）3是胍盐，B = M是二价金属离子（Mn，Fe，Co，Ni，Cu或Zn），X是甲酸盐HCOO。取决于金属，可以通过扩散或水热方法从水或富水溶液中合成这些化合物。五个元素（Mn，Fe，Co，Ni和Zn）在正交空间群Pnna中是同构的且结晶的，而在Pna21中则是Cu的。在钙钛矿结构中，八面体配位的金属离子通过抗-甲酸根桥键连接，从而形成阴离子NaCl型[MACHTUNGTRENUNG（HCOO）3]骨架，胍基存在于骨架的近立方腔中。 Cu 2+的Jahn–Teller效应导致扭曲的阴离子型Cu-甲酸酯骨架，可以将其视为通过长的轴向CuO键连接的短基础CuO键的Cu-甲酸酯链。这些材料显示出比其他金属-有机钙钛矿系列[AmineH] [MACHTUNGTRENUNG（HCOO）3]更高的热稳定性，该系列由有机单铵阳离子（AmineH +）模板化，这是由于胍和框架甲酸酯之间具有更强的氢键作用。磁性研究表明，五个磁性构件（除Zn以外）均显示自旋倾斜的反铁磁性，其Nel温度为8.8（Mn），10.0（Fe），14.2（Co），34.2（Ni）和4.6 K（Cu） 。除一般的自旋倾斜反铁磁性外，Fe化合物在50 kOe内显示出两个等温转变（自旋翻转和自旋翻转至顺磁性相）。 Co成员具有相当大的倾斜角度。 Cu构件是具有低尺寸特征的磁性系统，并且显示出缓慢的磁弛豫，其可能是由畴动力学引起的。

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