Molecular Conductors from Neutral-Radical Charge-Transfer Salts: Ppreparation and Characterization of an I Doped Hexagonal Phase of 1, 2, 3, 5-dithiadiazolyl ([HCN2S2].)

C. D. Bryan, A. W. Cordes, R. C. Haddon, T. T.M. Palstra, A. S. Perel, L. F. Schneemeyer, J. V. Waszczak, R. G. Hicks, D. K. Kennepohl, C. D. MacKinnon, R. T. Oakley, S. R. Scott

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72 Citations (Scopus)

Abstract

Sublimation of 1, 2, 3, 5-dithiadiazolyl in vacuo affords a triclinic phase of the dimer [HCN2S2]2. The crystals belong to the space group P1, a = 6.816(3), b = 13.940(2), c = 14.403(3) Å, α = 116.830(14), β = 98.64(3), γ = 99.18(3)°, FW = 212.4 (for [HCN2S2]2·[N2]0.08), Z = 6. The crystal structure consists of stacked dimers, with three dimers per asymmetric unit. Pairs of asymmetric units, related by an inversion center, generate a pinwheel motif consisting of six dimers. The columnar structure associated with these pinwheels forms close-packed sets of “molecular tubes”. Cosublimation of the radical in the presence of iodine in the mole ratio (HCN2S2:I = 5:1) yields an iodine-doped hexagonal phase of composition [HCN2S2]6[I]1.1- Crystals of this material belong to the space group P61 a = b = 14.132(16), c = 3.352(5) Å, FW = 128.20, Z = 6. The crystal structure consists of sixfold pinwheels in which the now evenly spaced HCN2S2 rings form a spiral about the 6i axis. The iodine atoms lie within the columnar cavity of the pinwheels in a disordered array wrapped tightly about the sixfold screw axis. The single-crystal conductivity of the doped material is 15 S cm-1 at room temperature. Raman spectroscopic and magnetic susceptibility measurements on the doped material are reported.

Original languageEnglish
Pages (from-to)1205-1210
Number of pages6
JournalJournal of the American Chemical Society
Volume116
Issue number4
DOIs
Publication statusPublished - 1 Feb. 1994

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