1. The Role of Coulomb Interactions for Spin Crossover Behaviors and Crystal Structural Transformation in Novel Anionic Fe(III) Complexes from a π-Extended ONO Ligand
- Author
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Yasuaki Einaga, Takashi Yamamoto, Kazuyuki Takahashi, Takahiro Sakurai, Yoshihito Shiota, Hitoshi Ohta, Kazunari Yoshizawa, and Suguru Murata
- Subjects
crystal structural transformation ,Coordination sphere ,General Chemical Engineering ,010402 general chemistry ,01 natural sciences ,Inorganic Chemistry ,Crystal ,chemistry.chemical_compound ,spin crossover ,Computational chemistry ,Spin crossover ,Coulomb ,lcsh:QD901-999 ,Molecule ,General Materials Science ,Coulomb interaction ,π-stacking interaction ,mononuclear Fe(III) complex ,anionic complex ,ONO tridentate ligand ,Tetramethylammonium ,010405 organic chemistry ,Ligand ,Electric potential energy ,Condensed Matter Physics ,0104 chemical sciences ,Crystallography ,chemistry ,lcsh:Crystallography - Abstract
To investigate the π-extension effect on an unusual negative-charged spin crossover (SCO) FeIII complex with a weak N2O4 first coordination sphere, we designed and synthesized a series of anionic FeIII complexes from a π-extended naphthalene derivative ligand. Acetonitrile-solvate tetramethylammonium (TMA) salt 1 exhibited an SCO conversion, while acetone-solvate TMA salt 2 was in a high-spin state. The crystal structural analysis for 2 revealed that two-leg ladder-like cation-anion arrays derived from π-stacking interactions between π-ligands of the FeIII complex anion and Coulomb interactions were found and the solvated acetone molecules were in one-dimensional channels between the cation-anion arrays. A desolvation-induced single-crystal-to-single-crystal transformation to desolvate compound 2’ may be driven by Coulomb energy gain. Furthermore, the structural comparison between quasi-polymorphic compounds 1 and 2 revealed that the synergy between Coulomb and π-stacking interactions induces a significant distortion of coordination structure of 2.
- Published
- 2016