Intrinsic and Environmental Effects in the Structure and Magnetic Properties of Organic Molecular Magnets: Bis(imino)nitroxide

Abstract

The structure, conformational behavior, and magnetic coupling constant of a prototypical organic molecular magnet (the bis(imino)nitroxide) have been investigated in vacuo and in solution, combining a recent density functional theory/Hartree−Fock model with a refined continuum description of the solvent. Comparison with previous sophisticated computations for a simplified model shows that our approach provides reliable magnetic couplings for a wide range (0−2000 cm-1) of interactions between the radical subunits. The computations performed for the true compound at the experimental conformation show that structural and magnetic parameters are in remarkable agreement with experiment. Solvent effects are negligible concerning the magnetic coupling but modify the conformational behavior leading to an inter-ring torsional angle in better agreement with the experimental value.