Structural, Magnetic, and Charge Transport Properties of Bis[(5,10,15,20-tetramethylporphyrinato)palladium(II)] Perrhenate, [Pd(tmp)]2[ReO4]

Ellen M. McGhee, Brian M. Hoffman*, James A. Ibers

*Corresponding author for this work

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Abstract

Electrochemical oxidation of (5,10,15,20-tetramethylporphyrinato)palladium(II), Pd(tmp), in the presence of the perrhenate ion affords the new molecular conductor [Pd(tmp)]2[ReO4]. The compound is composed of partially oxidized (+1/2) Pd(tmp) cations stacked metal-over-metal (Pd-Pdav = 3.373 (4) Å) and surrounded by chains of ReO4 anions. Single-crystal room-temperature conductivity along the needle (crystallographic c) axis averages 30 Ω-1 cm-1 and may be fit to an expression that describes a semiconductor with temperature-dependent carrier mobility, σ = σ0T-a exp(-ΔE/kaT) (ΔE = 0.10 (2) eV; α = 2.2 (5)). ESR measurements confirm the tmp ligand as the site of oxidation. The compound crystallizes in space group [formula omited] of the tetragonal system with two formula units in a cell of dimensions a = 16.778 (6) Å and c = 6.723 (3) Å (V = 1892 Å3) at 110 K. Full-matrix least-squares refinement of 67 variables gives a final value of 0.187 for the R index on F2 for 2404 unique observations and a value of 0.090 for the R index on F for the 1179 observations having Fo2 > 3σ(Fo2).

Original languageEnglish (US)
Pages (from-to)2162-2165
Number of pages4
JournalInorganic chemistry
Volume30
Issue number9
DOIs
StatePublished - May 1 1991

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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