Molecular Conductors from Neutral-Radical Charge-Transfer Salts - Preparation and Characterization of an Iodine-Doped Hexagonal Phase of 1,2,3,5-Dithiadiazolyl ([Hcn2s2](center-Dot))

by Bryan, Clinton Dave; Cordes, A. Wallace; Haddon, Robert C.; Hicks, Robin G.; Kennepohl, Dietmar K.; Mackinnon, Craig D.; Oakley, Richard T.; Palstra, Thomas T. M.; Perel, A. S.; Scott, Syrona Renae Horton; Schneemeyer, Lynn F.; Waszczak, Joseph V.

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=8.816(3), b=13.940(2), c=14.403(3) Angstrom a=3 116.830(14),beta=98.64(3), gamma 99.18(3)degrees, FW=212.4 (for [HCN2S2](2). [N-2](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 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 P6(1), a=b=14.132(16), c=3.352(5) Angstrom, 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 6(1) 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.

Journal of the American Chemical Society
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1520-5126; 0002-7863