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Solvent Dependent Spin‐Crossover and Photomagnetic Properties in an Imidazolylimine Fe II Complex
Author(s) -
Archer Rosanna J.,
Scott Hayley S.,
Polson Matthew I.J.,
Mathonière Corine,
Rouzières Mathieu,
Clérac Rodolphe,
Kruger Paul E.
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201900522
Subject(s) - spin crossover , crystallography , denticity , chemistry , spin transition , magnetic susceptibility , ligand (biochemistry) , molecule , materials science , crystal structure , biochemistry , receptor , organic chemistry
The synthesis and physico‐chemical characterization of an Fe II complex [Fe( L1 ) 3 ](ClO 4 ) 2 ⋅CH 3 CN⋅0.5H 2 O, 1 , incorporating a bidentate imidazolylimine‐based ligand are reported. Complex 1 crystallises as the mer ‐isomer and the crystal lattice is replete with hydrogen bonding interactions between ClO 4 − anions, solvent molecules and imidazole N‐H groups. Variable‐temperature structural, magnetic, photomagnetic and optical reflectivity techniques have been deployed to fully characterise the spin‐crossover (SCO) behaviour in 1 along with its desolvated phase, 1⋅desolv . Variable‐temperature (1.8–300 K) magnetic‐susceptibility measurements reveal a broad two‐step full SCO for 1 ( T 1/2 =158 and 184 K) and photomagnetic experiments at 10 K under white‐light irradiation revealed complete photo‐induced SCO. 1⋅desolv displays considerably different magnetic behaviour with sharp single‐step SCO accompanied by a thermal hysteresis ( T 1/2↑ =105 K, T 1/2↓ =95 K) in addition to full photo‐induced SCO at lower temperatures.
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