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

Suguru Murata, Kazuyuki Takahashi, Takahiro Sakurai, Hitoshi Ohta, Takashi Yamamoto, Yasuaki Einaga, Yoshihito Shiota, Kazunari Yoshizawa

Research output: Contribution to journalArticle

6 Citations (Scopus)

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.

Original languageEnglish
Article number49
JournalCrystals
Volume6
Issue number5
DOIs
Publication statusPublished - 2016 May 1

Keywords

  • Anionic complex
  • Coulomb interaction
  • Crystal structural transformation
  • Mononuclear Fe(III) complex
  • ONO tridentate ligand
  • Spin crossover
  • π-stacking interaction

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Inorganic Chemistry

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