Thermal and Magnetic Field Switching in a Two-Step Hysteretic Mn III Spin Crossover Compound Coupled to Symmetry Breakings

A Mn spin crossover complex with atypical two-step hysteretic thermal switching at 74 K and 84 K shows rich structural-magnetic interplay and magnetic-field-induced spin state switching below 14 T with an onset below 5 T. The spin states, structures, and the nature of the phase transitions are eluci...

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Published in:Angewandte Chemie International Edition 2022-01, Vol.61 (4), p.e202114021
Main Authors: Dobbelaar, Emiel, Jakobsen, Vibe B, Trzop, Elzbieta, Lee, Minseong, Chikara, Shalinee, Ding, Xiaxin, Müller-Bunz, Helge, Esien, Kane, Felton, Solveig, Carpenter, Michael A, Collet, Eric, Morgan, Grace G, Zapf, Vivien S
Format: Article
Language:English
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Summary:A Mn spin crossover complex with atypical two-step hysteretic thermal switching at 74 K and 84 K shows rich structural-magnetic interplay and magnetic-field-induced spin state switching below 14 T with an onset below 5 T. The spin states, structures, and the nature of the phase transitions are elucidated via X-ray and magnetization measurements. An unusual intermediate phase containing four individual sites, where are in a pure low spin state, is observed. The splitting of equivalent sites in the high temperature phase into four inequivalent sites is due to a structural reorganization involving a primary and a secondary symmetry-breaking order parameter that induces a crystal system change from orthorhombic→monoclinic and a cell doubling. Further cooling leads to a reconstructive phase transition and a monoclinic low-temperature phase with two inequivalent low-spin sites. The coupling between the order parameters is identified in the framework of Landau theory.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202114021