Solvent Dependent Spin-Crossover and Photomagnetic Properties in an Imidazolylimine FeII Complex.
Rosanna J ArcherHayley S ScottMatthew I J PolsonCorine MathonièreMathieu RouzièresRodolphe CléracPaul E KrugerPublished in: Chemistry, an Asian journal (2019)
The synthesis and physico-chemical characterization of an FeII complex [Fe(L1)3 ](ClO4 )2 ⋅CH3 CN⋅0.5H2 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 ClO4 - 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 (T1/2 =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 (T1/2↑ =105 K, T1/2↓ =95 K) in addition to full photo-induced SCO at lower temperatures.
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