Hybrid molecular material exhibiting single-molecule magnet behavior and molecular conductivity

Hiroki Hiraga, Hitoshi Miyasaka, Kazuya Nakata, Takashi Kajiwara, Shinya Takaishi, Yugo Oshima, Hiroyuki Nojiri, Masahiro Yamashita

Research output: Contribution to journalArticlepeer-review

95 Citations (Scopus)

Abstract

Two unique materials based on Mn4 single-molecule magnet (SMM) clusters (ST = 9) and integer or non-integer average valent platinum maleonitriledithiolate (mnt2-) complexes, [{MnII 2MnIII2(hmp)6(MeCN) 2}{Pt(mnt)2}2][Pt(mnt)2] 2· 2MeCN (1) and [{MnII2Mn III2(hmp)6(MeCN)2}{Pt(mnt) 2}4][Pt(mnt)2]2 (2), were synthesized by the material diffusion method and electrochemical oxidation, respectively (hmp- = 2-hydroxymethylpyridinate). 1 and 2 are comprised of four and six [Pt(mnt)2]n- units, respectively, in addition to a common MnII2Mn III2 double-cuboidal unit, [MnII 2-MnIII2(hmp)6(MeCN) 2]4+ (hereinafter [Mn4]4+). Among the [Pt(mnt)2]n- units, two units in 1 and four units in 2 are coordinated with the [Mn4]4+ unit, forming a 1D chain of {-[Mn4]-[Pt(mnt)2]2-} for 1 and a discrete subunit of {[Pt(mnt)2]2-[Mn4]-[Pt(mnt) 2]2} for 2. The other two [Pt(mnt)2] n- units, occupying void space of the packing, form a stacking column with the coordinating [Pt(mnt)2]n- units, finally constructing hybrid frames of aggregates consisting of [Mn4] 4+ units and [Pt(mnt)2]n- units. Electronic conductivity measurements revealed that 1 is an insulator and 2 is a semiconductor with σ = 0.22 S·cm-1 at room temperature and an activation energy of 136 meV. Detailed magnetic measurements proved that the [Mn4]4+ units in 1 and 2 behave as SMMs with an S T = 9 ground state at low temperatures. There is no significant interaction between [Mn4]4+ units and [Pt(mnt) 2]n- units, but interactions between localized spins of [Pt(mnt)2]n- were detected even in 2 at low temperatures where the conductivity is electronically insulated. 2 is the first example of a hybridized material exhibiting SMM behavior and electronic conductivity.

Original languageEnglish
Pages (from-to)9661-9671
Number of pages11
JournalInorganic chemistry
Volume46
Issue number23
DOIs
Publication statusPublished - 2007 Nov 12

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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