Issue 30, 2015

Novel Fe(ii) spin crossover complexes involving a chalcogen-bond and π-stacking interactions with a paramagnetic and nonmagnetic M(dmit)2 anion (M = Ni, Au; dmit = 4,5-dithiolato-1,3-dithiole-2-thione)

Abstract

To introduce both an inter-sulphur atom and π-stacking interaction between a spin crossover (SCO) cation and paramagnetic anion, we designed and synthesised two novel Fe(II) SCO compounds involving a terpyridine-type thiazole containing ligand with the paramagnetic Ni(dmit)2 and nonmagnetic Au(dmit)2 anion (dmit = 4,5-dithiolato-1,3-dithiole-2-thione). The temperature variations of magnetic susceptibility and Mössbauer spectroscopy revealed that both complexes exhibited an almost complete SCO conversion, and moreover, the Ni(dmit)2 anion was in a paramagnetic state down to 2 K. The crystal structures for the Ni(dmit)2 complex at 213 and 400 K indicated that the chalcogen-bond and π-stacking interaction would be enhanced by the electrostatic interaction between the cation and anion, preventing the π-radicals from dimerising. The light-induced excited spin state trapping effect was observed at 5 K.

Graphical abstract: Novel Fe(ii) spin crossover complexes involving a chalcogen-bond and π-stacking interactions with a paramagnetic and nonmagnetic M(dmit)2 anion (M = Ni, Au; dmit = 4,5-dithiolato-1,3-dithiole-2-thione)

Supplementary files

Article information

Article type
Paper
Submitted
27 Mar 2015
Accepted
05 May 2015
First published
13 May 2015

J. Mater. Chem. C, 2015,3, 7858-7864

Author version available

Novel Fe(II) spin crossover complexes involving a chalcogen-bond and π-stacking interactions with a paramagnetic and nonmagnetic M(dmit)2 anion (M = Ni, Au; dmit = 4,5-dithiolato-1,3-dithiole-2-thione)

M. Okai, K. Takahashi, T. Sakurai, H. Ohta, T. Yamamoto and Y. Einaga, J. Mater. Chem. C, 2015, 3, 7858 DOI: 10.1039/C5TC00859J

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