Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
The Chemical Society of Japan Award for Creative Work for 2010
Development of π-Electron Systems Based on [M(dmit)2] (M = Ni and Pd; dmit: 1,3-dithiole-2-thione-4,5-dithiolate) Anion Radicals
Reizo Kato
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2014 Volume 87 Issue 3 Pages 355-374

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Abstract

Molecular conductors based on [M(dmit)2] (M = Ni and Pd) present a variety of π electron systems that pave the way for a higher stage of solid-state science. Supramolecular interactions between [Ni(dmit)2] anion and halogen-containing cations provide bilayer systems that are characterized by coexistence of two crystallographically independent anion layers with different molecular arrangements and contrasting (for example, metal/insulator and ferromagnetic/antiferromagnetic) properties. In [Pd(dmit)2] salts in the Mott insulating state, a small energy difference between HOMO and LUMO coupled with strong dimerization affords HOMO–LUMO band inversion. The dimer units [Pd(dmit)2]2 form a triangular lattice, and interplay of strong electron correlation and spin frustration generates a wide variety of magnetic/charge states including antiferromagnetic long-range order, quantum spin liquid, charge order, and valence bond order, depending on counter cations. The cation dependence is attributed to a systematic arch-shaped molecular distortion that tunes the anisotropy of interdimer transfer integrals. This means that the [Pd(dmit)2] molecular skeleton is sufficiently flexible within the crystal field, and molecular degrees of freedom play an important role in fine tuning of the electronic state.

Anion radical salts based on the metal dithiolene complex [M(dmit)2] (M = Ni and Pd) present a variety of π electron systems that go beyond the framework of conventional molecular conductors, depending on the selection of counter cation. Fullsize Image
 
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