Crystals 2016, 6(5), 49; https://doi.org/10.3390/cryst6050049
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 1, Kazuyuki Takahashi 1,*
, Takahiro Sakurai 2, Hitoshi Ohta 3, Takashi Yamamoto 4, Yasuaki Einaga 4, Yoshihito Shiota 5 and Kazunari Yoshizawa 5
, Takahiro Sakurai 2, Hitoshi Ohta 3, Takashi Yamamoto 4, Yasuaki Einaga 4, Yoshihito Shiota 5 and Kazunari Yoshizawa 5
1
Department of Chemistry, Graduate School of Science, Kobe University, 1-1 Rokkodai, Nada-ku, Kobe, Hyogo 657-8501, Japan
2
Center for Support of Education and Research Activities, Kobe University, 1-1 Rokkodai, Nada-ku, Kobe, Hyogo 657-8501, Japan
3
Molecular Photoscience Research Center, Kobe University, 1-1 Rokkodai, Nada-ku, Kobe, Hyogo 657-8501, Japan
4
Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan
5
Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
*
Author to whom correspondence should be addressed.
Academic Editor: Martin T. Lemaire
Received: 30 March 2016 / Revised: 27 April 2016 / Accepted: 28 April 2016 / Published: 3 May 2016
(This article belongs to the Special Issue High Spin Molecules)
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. View Full-TextKeywords:
spin crossover; Coulomb interaction; π-stacking interaction; crystal structural transformation; mononuclear Fe(III) complex; anionic complex; ONO tridentate ligand
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Murata, S.; Takahashi, K.; Sakurai, T.; Ohta, H.; Yamamoto, T.; Einaga, Y.; Shiota, Y.; Yoshizawa, K. 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. Crystals 2016, 6, 49.
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