Rationalizing Spin-Crossover Properties of Substituted Fe (II) Complexes.

ABSTRACT: We investigate spin-state transitions in a series of 24 [Fe^II(bpp^X)₂]²⁺ spin-crossover (SCO) complexes using density functional theory (DFT). The TPSSh/def2-TZVP approach demonstrates reasonable accuracy in predicting spin-state energetics compared to other functionals, though significant deviations persist in transition temperature (T_1/2) estimates. Temperature-dependent and quasi-harmonic corrections for low-frequency vibrational contributions to enthalpic and entropic terms yielded only marginal improvements. To improve T_1/2 prediction accuracy, we develop electronic descriptors based on effective fragment orbitals (EFOs) and their occupations, quantifying ligand σ-donation and π-acceptor characteristics tha

SUBMITTER: Comas-Vila G 

PROVIDER: S-EPMC12326360 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature