An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(III)

Miki Nishi, Ryuta Ishii, Mitsuo Ikeda, Noriaki Hanasaki, Norihisa Hoshino, Tomoyuki Akutagawa, Michinori Sumimoto, Masaki Matsuda

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    1 Citation (Scopus)

    Abstract

    A porphyrin-based octahedrally ligated complex with high-spin iron(iii) was designed, and the resulting electrically conducting crystal TPP[FeIII(tbp)Br2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) was synthesised. Although TPP[Fe(tbp)Br2]2 was isostructural to the reported TPP[Fe(Mc)L2]2 systems (Mc = macrocyclic ligands such as phthalocyanine (Pc) or tbp; and L = CN, Cl, or Br), the bond lengths between Fe and ligands in the [Fe(tbp)Br2] unit were evidently longer than those in the other units, because of the different spin states of Fe: high-spin in TPP[Fe(tbp)Br2]2 and low-spin in others. The magnetic anisotropy observed in the low-spin state vanished when the Fe is in the high-spin state. Based on reports for Pc-based systems, the negative magnetoresistance (MR) effect for TPP[Fe(tbp)Br2]2 was expected to be smaller than that for TPP[Fe(tbp)(CN)2]2. However, the former showed a giant negative MR effect similar to or larger than the latter, suggesting that the nature of iron is a crucial factor for the electrical properties of porphyrin-based materials.

    Original languageEnglish
    Pages (from-to)4070-4075
    Number of pages6
    JournalDalton Transactions
    Volume47
    Issue number12
    DOIs
    Publication statusPublished - 2018

    ASJC Scopus subject areas

    • Inorganic Chemistry

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