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Insight into Structure: Function Relationships in a Molecular Spin‐Crossover Crystal, from a Related Weakly Cooperative Compound
Author(s) -
Elhaïk Jérôme,
Kilner Colin A.,
Halcrow Malcolm A.
Publication year - 2014
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.201402623
Subject(s) - chemistry , spin crossover , crystallography , spin (aerodynamics) , salt (chemistry) , crystal structure , spin transition , chemical physics , thermodynamics , physics
The ClO 4 – salt of [Fe L 2 ] 2+ { L = 2,6‐bis(3‐methylpyrazol‐1‐yl)pyridine} undergoes very gradual thermal spin‐crossover centered just below room temperature. In contrast, the BF 4 – salt of the same complex exhibits an abrupt and structured spin‐transition at lower temperature, with a complicated structural chemistry. The difference can be attributed to a much larger change in molecular structure between the spin states of the complex in the more cooperative BF 4 – salt, leading to an increased kinetic barrier for their interconversion. Consistent with that suggestion, the high‐spin and low‐spin structures of weakly cooperative [Fe L 2 ][ClO 4 ] 2 are almost superimposable.