Solvent Effects on the Spin Crossover Properties of Iron(II) Imidazolylimine Complexes
Darunee Sertphon,
Phimphaka Harding,
Keith S. Murray,
Boujemaa Moubaraki,
Suzanne M. Neville,
Lujia Liu,
Shane G. Telfer,
David J. Harding
Affiliations
Darunee Sertphon
Functional Materials and Nanotechnology Center of Excellence, Walailak University, Thasala, Nakhon Si Thammarat 80160, Thailand
Phimphaka Harding
Functional Materials and Nanotechnology Center of Excellence, Walailak University, Thasala, Nakhon Si Thammarat 80160, Thailand
Keith S. Murray
School of Chemistry, Monash University, Clayton, VIC 3800, Australia
Boujemaa Moubaraki
School of Chemistry, Monash University, Clayton, VIC 3800, Australia
Suzanne M. Neville
School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia
Lujia Liu
MacDiarmid Institute for Advanced Materials and Nanotechnology, Institute of Fundamental Sciences, Massey University, Palmerston North 4442, New Zealand
Shane G. Telfer
MacDiarmid Institute for Advanced Materials and Nanotechnology, Institute of Fundamental Sciences, Massey University, Palmerston North 4442, New Zealand
David J. Harding
Functional Materials and Nanotechnology Center of Excellence, Walailak University, Thasala, Nakhon Si Thammarat 80160, Thailand
A series of Fe(II) complexes, fac-[Fe(4-ima-Bp)3](Y)2⋅sol (Y = ClO4; sol = 3EtOH 1, 3MeOH 2; Y= BF4; sol = EtOH⋅4H2O 3, 4H2O 4 and 3.5MeCN 5) have been prepared and structurally and magnetically characterized. The low temperature structures of 1, 2 and 5 have been determined by X-ray crystallography with LS Fe(II) centres found in all cases. Extensive C⁻H···π interactions between the cations form 2D layers, which are linked to one another through N-H···O and O-H···O hydrogen bonds, resulting in high cooperativity. Despite 5 containing MeCN, N-H···O/F hydrogen bonds, and C⁻H···π and π-π interactions combine to give similar 2D layers. Magnetic measurements reveal moderately abrupt spin crossover for 1-4; becoming more gradual and only 50% complete in 1 due to solvent loss. The MeCN solvate shows more gradual SCO and reinforces how subtle changes in packing can significantly influence SCO behaviour.
