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Bis(formazanate)iron(II) complexes undergo a thermally induced S = 0 to S = 2 spin transition in solution. Here we present a study of how steric effects and π-stacking interactions between the triarylformazanate ligands affect the spin-crossover behavior, in addition to electronic substituent effects. Moreover, the effect of increasing the denticity of the formazanate ligands is explored by including additional OMe donors in the ligand ( 7 ). In total, six new compounds ( 2 - 7 ) have been synthesized and characterized, both in solution and in the solid state, via spectroscopic, magnetic, and structural analyses. The series spans a broad range of spin-crossover temperatures ( T  1/2 ) for the LS ⇌ HS equilibrium in solution, with the exception of compound 6 which remains high-spin ( S = 2) down to 210 K. In the solid state, 6 was shown to exist in two distinct forms: a tetrahedral high-spin complex ( 6a , S = 2) and a rare square-planar structure with an intermediate-spin state ( 6b , S = 1). SQUID measurements, 57 Fe Mössbauer spectroscopy, and differential scanning calorimetry indicate that in the solid state the square-planar form 6b undergoes an incomplete spin-change-coupled isomerization to tetrahedral 6a . The complex that contains additional OMe donors ( 7 ) results in a six-coordinate (NNO) 2 Fe coordination geometry, which shifts the spin-crossover to significantly higher temperatures ( T  1/2 = 444 K). The available experimental and computational data for 7 suggest that the Fe···OMe interaction is retained upon spin-crossover. Despite the difference in coordination environment, the weak OMe donors do not significantly alter the electronic structure or ligand-field splitting, and the occurrence of spin-crossover (similar to the compounds lacking the OMe groups) originates from a large degree of metal-ligand π-covalency.

Widening the Window of Spin-Crossover Temperatures in Bis(formazanate)iron(II) Complexes via Steric and Noncovalent Interactions