X-ray structures of the halo-substituted complexes [FeIII(5-X-salMeen)2]ClO4 (X=F, Cl, Br, I) [salMeen=N-methyl-N-(2-aminoethyl)salicylaldiminate]at RT have revealed the presence of two discrete HS complex cations in the crystallographic asymmetric unit with two perchlorate counter ions linking them by N−Hamine⋅⋅⋅Operchlorate interactions. At 90 K, the two complex cations are distinctly HS and LS, a rare crystallographic observation of this coexistence in the FeIII-salRen (R=alkyl) spin-crossover (SCO) system. At both temperatures, crystal packing shows dimerization through C−Himine⋅⋅⋅Ophenolate interactions, a key feature for SCO cooperativity. Moreover, there are noncovalent contacts between the complex cations through type-II halogen-halogen bonds, which are novel in this system. The magnetic profiles and Mössbauer spectra concur with the structural analyses and reveal 50 % SCO of the type [HS-HS]↔[HS-LS] with a broad plateau. In contrast, [FeIII(5-Cl-salMeen)2]BPh4⋅2MeOH is LS and exhibits a temperature-dependent crystallographic phase transition, exemplifying the influence of lattice solvents and counter ions on SCO.
- crystallographic phase transition
- electronic and electrochemical processes
- ferric spin crossover
- noncovalent interactions
- spin-transition plateau
ASJC Scopus subject areas
- Organic Chemistry