Electronic state of a conducting single molecule magnet based on Mn-salen type and Ni-dithiolene complexes

Kazuya Kubo, Takuya Shiga, Takashi Yamamoto, Akiko Tajima, Taro Moriwaki, Yuka Ikemoto, Masahiro Yamashita, Elisa Sessini, Maria Laura Mercuri, Paola Deplano, Yasuhiro Nakazawa, Reizo Kato

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23 Citations (Scopus)

Abstract

The electrochemical oxidation of an acetone solution containing [Mn III (5-MeOsaltmen)(H2O)]2(PF6) 2 (5-MeOsaltmen2- = N,N′-(1,1,2,2- tetramethylethylene)bis(5-methoxysalicylideneiminate)) and (NBu 4)[Ni(dmit)2] (dmit2- = 2-thioxo-1,3-dithiole- 4,5-dithiolate) afforded a hybrid material, [Mn(5-MeOsaltmen)(acetone)] 2[Ni(dmit)2]6 (1), in which [Mn 2]2+ single-molecule magnets (SMMs) with an ST = 4 ground state and [Ni(dmit)2]n- molecules in a charge-ordered state (n = 0 or 1) are assembled in a layer-by-layer structure. Compound 1 crystallizes in the triclinic space group P1̄ with an inversion center at the midpoint of the Mn⋯Mn dimer. The [Mn2] 2+ unit has a typical nonplanar Mn(III) dimeric core and is structurally consistent with previously reported [Mn2] SMMs. The six [Ni(dmit)2]n- (n = 0 or 1) units have a square-planar coordination geometry, and the charge ordering among them was assigned on the basis of ν(C=C) in IR reflectance spectra (1386, 1356, 1327, and 1296 cm -1). The [Mn2]2+ SMM and [Ni(dmit) 2]n- units aggregate independently to form hybrid frames. Electronic conductivity measurements revealed that 1 behaved as a semiconductor (ρrt = 2.1 × 10-1 ω·cm -1, Ea = 97 meV) at ambient pressure and as an insulator at 1.7 GPa (ρ1.7GPa = 4.5 ω·cm-1, E a = 76 meV). Magnetic measurements indicated that the [Mn 2]2+ units in 1 behaved as ST = 4 SMMs at low temperatures.

Original languageEnglish
Pages (from-to)9337-9344
Number of pages8
JournalInorganic chemistry
Volume50
Issue number19
DOIs
Publication statusPublished - 2011 Oct 3

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Kubo, K., Shiga, T., Yamamoto, T., Tajima, A., Moriwaki, T., Ikemoto, Y., Yamashita, M., Sessini, E., Mercuri, M. L., Deplano, P., Nakazawa, Y., & Kato, R. (2011). Electronic state of a conducting single molecule magnet based on Mn-salen type and Ni-dithiolene complexes. Inorganic chemistry, 50(19), 9337-9344. https://doi.org/10.1021/ic200863c