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The transition between spin states in d-block metal complexes has important ramifications for their structure and reactivity, with applications ranging from information storage materials to understanding catalytic activity of metalloenzymes. Tuning the ligand field (Δ O ) by steric and/or electronic effects has provided spin-crossover compounds for several transition metals in the periodic table, but this has mostly been limited to coordinatively saturated metal centers in octahedral ligand environments. Spin-crossover complexes with low coordination numbers are much rarer. Here we report a series of four-coordinate, (pseudo)tetrahedral Fe(II) complexes with formazanate ligands and demonstrate how electronic substituent effects can be used to modulate the thermally induced transition between S = 0 and S = 2 spin states in solution. All six compounds undergo spin-crossover in solution with T  1/2 above room temperature (300-368 K). While structural analysis by X-ray crystallography shows that the majority of these compounds are low-spin in the solid state (and remain unchanged upon heating), we find that packing effects can override this preference and give rise to either rigorously high-spin ( 6 ) or gradual spin-crossover behavior ( 5 ) also in the solid state. Density functional theory calculations are used to delineate the empirical trends in solution spin-crossover thermodynamics. In all cases, the stabilization of the low-spin state is due to the π-acceptor properties of the formazanate ligand, resulting in an "inverted" ligand field, with an approximate "two-over-three" splitting of the d-orbitals and a high degree of metal-ligand covalency due to metal → ligand π-backdonation. The computational data indicate that the electronic nature of the para -substituent has a different influence depending on whether it is present at the C-Ar or N-Ar rings, which is ascribed to the opposing effect on metal-ligand σ- and π-bonding.

Electronic Control of Spin-Crossover Properties in Four-Coordinate Bis(formazanate) Iron(II) Complexes