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

  Condensed Molecular Materials Laboratory, RIKEN

抄録

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.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 87 (3), 355-374, 2014-03

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360002219096925184
• NII論文ID: 130004153288
• DOI: 10.1246/bcsj.20130290
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/87/3/355/56276802/bcsj.20130290.pdf
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