Spectroscopic Identification of Disordered Molecular Cations in Defect Perovskite-Like A Ln (HCO 2 )(C 2 O 4 ) 1.5 ( Ln =Tb-Er) Phases
Spectroscopic Identification of Disordered Molecular Cations in Defect Perovskite-Like A Ln (HCO 2 )(C 2 O 4 ) 1.5 ( Ln =Tb-Er) Phases
复制标题
缺陷类钙钛矿 A Ln (HCO 2 )(C 2 O 4 ) 1.5 ( Ln =Tb-Er) 相中无序分子阳离子的光谱鉴定
DOI：
10.1002/ejic.202100591
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发表时间：
2021
影响因子：
2.3
通讯作者：
Burley L
中科院分区：
文献类型：
--
作者：
Burley L
本文报道了一系列新的溶剂热合成的ALn（HCO 2）（C2 O 4）1.5（A=[（CH 3）2NH 2]+，Ln 3 += Tb 3 +-Er 3+）化合物。这些钙钛矿相结合了联合收割机一价和二价配体，这使得在混合钙钛矿样化合物中A+和B3+阳离子的组合稀少。配体的比例导致有序的阴离子空位，其与草酸根连接基沿着c轴交替。A位阳离子是无序的，并且无法在晶体学上识别，这可能是由于与最近报道的AEr（HCO 2）2（C2 O 4）相相比，这些框架的孔更大。由元素组成支持的中子和红外光谱使这些阳离子能够被鉴定为[（CH 3）2NH 2]+分子。磁性测量表明，这些材料具有弱的反铁磁相互作用，但保持顺磁性到1.8 K。
This work reports a new series of ALn(HCO2)(C2O4)1.5(A=[(CH3)2NH2]+andLn3+=Tb3+‐Er3+) compounds made solvothermally. TheseCmcephases combine monovalent and divalent ligands, which enables a scarce combination of A+and B3+cations in a hybrid perovskite‐like compound. The ratio of ligands leads to ordered anion vacancies, which alternate with oxalate linkers along thec‐axis. The A‐site cations are disordered and cannot be identified crystallographically, likely a result of the larger pores of these frameworks compared to the recently reported AEr(HCO2)2(C2O4) phases. Neutron and infrared spectroscopy, supported by elemental composition, enables these cations to be identified as [(CH3)2NH2]+molecules. Magnetic property measurements suggest these materials have weak antiferromagnetic interactions but remain paramagnetic to 1.8 K.