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Crystals 2016, 6(5), 49; doi: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

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)
View Full-Text   |   Download PDF [3129 KB, uploaded 3 May 2016]   |  

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-Text
Keywords: spin crossover; Coulomb interaction; π-stacking interaction; crystal structural transformation; mononuclear Fe(III) complex; anionic complex; ONO tridentate ligand spin crossover; Coulomb interaction; π-stacking interaction; crystal structural transformation; mononuclear Fe(III) complex; anionic complex; ONO tridentate ligand
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

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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