Spin-Crossover in a Pseudo-tetrahedral Bis(formazanate) Iron Complex

Spin-crossover in a pseudo-tetrahedral bis(formazanate) iron(II) complex (1) is described. Structural, magnetic, and spectroscopic analyses indicate that this compound undergoes thermal switching between an S=0 and an S=2 state, which is very rare in four-coordinate complexes. The transition to the high-spin state is accompanied by an increase in Fe-N bond lengths and a concomitant contraction of intraligand N-N bonds. The latter suggests that stabilization of the low-spin state is due to the π-acceptor properties of the ligand. One-electron reduction of 1 leads to the formation of the corresponding anion, which contains a low-spin (S=1/2) Fe(I) center. The findings are rationalized by electronic structure calculations using density functional theory.