Pybox-Iron(II) Spin-Crossover Complexes with Substituent Effects from the 4-Position of the Pyridine Ring (Pybox = 2,6-Bis(oxazolin-2-yl)pyridine)

Spin-crossover (SCO) behavior of a series of [Fe(X-pybox)2](ClO4)2 was investigated, where X-pybox stands for 4-X-substituted 2,6-bis(oxazolin-2-yl)pyridine with X = H, Cl, Ph, CH3O, and CH3S. We confirmed that the mother compound [Fe(H-pybox)2](ClO4)2 underwent SCO above room temperature. After X was introduced, the SCO temperatures (T1/2) were modulated as 310, 230, and 330 K for X = Cl, Ph, and CH3S, respectively. The CH3O derivative possessed the high-spin state down to 2 K. Crystallographic analysis for X = H, Cl, CH3O, and CH3S was successful, being consistent with the results of the magnetic study. Distorted coordination structures stabilize the HS (high-spin) state, and the highest degree of the coordination structure distortion is found in the CH3O derivative. A plot of T1/2 against the Hammett substituent constant σp showed a positive relation. Solution susceptometry was also performed to remove intermolecular interaction and rigid crystal lattice effects, and the T1/2’s were determined as 260, 270, 240, 170, and 210 K for X = H, Cl, Ph, CH3O, and CH3S, respectively, in acetone. The substituent effect on T1/2 became very distinct, and it is clarified that electron-donating groups stabilize the HS state.