Linear Chain Organometailic Donor-acceptor Complexes and One-dimensional Alloys. Synthesis and Structure of [(≡6-c6Me3H3)2M][c6(CN)6] (M = Fe, Ru)

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Abstract

Organometallic linear chain complexes [(i6-C6Me3H3)2M][C6(CN)6] (M = Fe, la; M = Ru, 2a) and [(76-C6Me6)2M][C6(CN)6] (M = Fe, lb; M = Ru, 2b) prepared from [(j76-arene)2M]2+ cations and [C6(CN)6]12” are described. Single-crystal X-ray studies show that la crystallizes in the space group R3, with a = 14.875 (5) A, c = 9.858 (4) k,V= 1889 (2) A3, p = 1.38 g cm”3, Z = 3, Ru = 0.047, and Rw= 0.056. The ruthenium analogue 2a also crystallizes in the space group R3, with a = 14.825 (5) A, c = 10.093 (3) A, V - 1921 (2) A3, p = 1.48 g cm”3, Z = 3, Ru= 0.026, and Rw= 0.031. Both complexes exhibit mixed stacks of alternating cations and anions with interplanar spacings less than the sum of the van der Waals radii. The complexes exhibit strong charge-transfer bands and are best described as “superionic” donor-acceptor (DA) complexes with nominally doubly charged (D2“A2+) ground states and (D“A+) excited states. The difference in the charge-transfer absorption energies for a given donor dianion is equivalent to the difference in the reduction potentials of the isostructural [(776-arene)2M]2-f cations in solution. Since la and 2a both crystallize in the R3 space group and exhibit different unit cell lengths along only the linear chain axis, mixed-metal linear chain complexes [(776-C6Me3H3)2Fe]x[()6-C6Me3H3)2Ru]1_;c[C6(CN)6] are readily prepared. These mixed-metal phases exhibit optical absorption intensities consistent with Beer’s law behavior, and the macroscopic optical properties can be tailored by control of the relative amounts of the iron and ruthenium chromophores.

Original languageEnglish (US)
Pages (from-to)754-762
Number of pages9
JournalOrganometallics
Volume6
Issue number4
DOIs
StatePublished - Apr 1 1987

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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