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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

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

Authors :
Yasuaki Einaga
Takashi Yamamoto
Kazuyuki Takahashi
Takahiro Sakurai
Yoshihito Shiota
Hitoshi Ohta
Kazunari Yoshizawa
Suguru Murata
Source :
Crystals; Volume 6; Issue 5; Pages: 49, Crystals, Vol 6, Iss 5, p 49 (2016)
Publication Year :
2016
Publisher :
MDPI, 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.

Details

Language :
English
ISSN :
20734352
Volume :
6
Issue :
5
Database :
OpenAIRE
Journal :
Crystals
Accession number :
edsair.doi.dedup.....23df6f4e7f0c1b03d7334ce0b5d22bfe