[MIII(dmit)2]--coordinated Mn III salen-type dimers (MIII = NiIII, Au III, dmit2 = 1,3-dithiol-2-thione-4,5-dithiolate): Design of single-component conducting single-molecule magnet-based materials

Hiroki Hiraga, Hitoshi Miyasaka, Rodolphe Clérac, Marc Fourmigué, Masahiro Yamashita

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56 Citations (Scopus)


Four linear-type tetranuclear complexes, [Mn(5-Rsaltmen){M(dmit) 2}]2 (R = MeO, M = Ni, 1a; M = Au, 1b; R = Me, M = Ni, 2a; M = Au, 2b), were synthesized and structurally characterized (5-Rsaltmen 2- = Λ/./V '-(1,1,2,2- tetramethylethylene)-bis(5- Rsalicylideneiminate), dmit2- = 1,3-dithiol-2-thione-4,5-dithiolate). These compounds crystallize in the same triclinic P1 space group (Z= 1) and have a similar molecular structure with a bridging array of [M-(dmit)-Mn-(0ph)2- Mn-(dmit)-M] and a packing feature where the respective sets of 1a/1b and 2a/2b are isomorphous. Intermolecular π-πlS ⋯ S contacts are observed between the coordinating [M(dmit)2]- moieties to form zigzag stair-like columns along the a axis direction. Hückel calculations revealed a strong intermolecular dimerization within the [Ni(dmit)2] column that makes them magnetically silent even at room temperature. Nevertheless, 1a and 2a with M = Ni behave as semiconductors with σΓ.t. = 7 × 1CΓ4 S·cm -1 and Ea = 182 meV for 1a and σΓ. t. = 1 × 10-4 S ·cm-1 and E a = 292 meV for 2a, while 1b and 2b with M = Au are insulators. As a result of the strong dimerization of the [Ni(dmit)2]- anions, the magnetic properties of 1a are essentially identical to those of 1b and 2b, which can be described as isolated Mn(lll) dimers, acting as single-molecule magnets (SMM). Meanwhile, the magnetic properties of 2a are dominated by the intermolecular Mn ⋯ Mn antiferromagnetic interactions via the singlet [Ni(dmit)2]22- dimer (JMN⋯MN/KB = -2.85 K), inducing a long-range antiferromagnetic order at TN = 6.4 K. The present systems are unique materials made of neutral single-component complexes that exhibit two major solid-state properties, that is, electrical conductivity and magnetism, varied as semiconductor/SMM for 1a, insulator/SMM for 1b and 2b, and semiconductor/ antiferromagnet for 2a by tuning metal center and partial structural modification.

Original languageEnglish
Pages (from-to)2887-2898
Number of pages12
JournalInorganic chemistry
Issue number7
Publication statusPublished - 2009

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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