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Spectroscopic Identification of Disordered Molecular Cations in Defect Perovskite‐Like A Ln (HCO 2 )(C 2 O 4 ) 1.5 ( Ln =Tb‐Er) Phases
Author(s) -
Burley Lydia G.,
Srivastava Anant Kumar,
Rudić Svemir,
Saines Paul J.
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100591
Subject(s) - chemistry , crystallography , oxalate , antiferromagnetism , divalent , lanthanide , infrared spectroscopy , paramagnetism , molecule , perovskite (structure) , neutron diffraction , ion , inorganic chemistry , crystal structure , physics , organic chemistry , quantum mechanics , condensed matter physics
This work reports a new series of A Ln (HCO 2 )(C 2 O 4 ) 1.5 (A=[(CH 3 ) 2 NH 2 ] + and Ln 3+ =Tb 3+ ‐Er 3+ ) compounds made solvothermally. These Cmce phases combine monovalent and divalent ligands, which enables a scarce combination of A + and B 3+ cations in a hybrid perovskite‐like compound. The ratio of ligands leads to ordered anion vacancies, which alternate with oxalate linkers along the c ‐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(HCO 2 ) 2 (C 2 O 4 ) phases. Neutron and infrared spectroscopy, supported by elemental composition, enables these cations to be identified as [(CH 3 ) 2 NH 2 ] + molecules. Magnetic property measurements suggest these materials have weak antiferromagnetic interactions but remain paramagnetic to 1.8 K.