Pressure enhanced conductivity in bis-1,2,3-thiaselenazolyl dimers

被引:49
作者
Beer, L
Brusso, JL
Haddon, RC
Itkis, ME
Kleinke, H
Leitch, AA
Oakley, RT [1 ]
Reed, RW
Richardson, JF
Secco, RA
Yu, XY
机构
[1] Univ Waterloo, Dept Chem, Waterloo, ON N2L 3G1, Canada
[2] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA
[3] Univ Calif Riverside, Ctr Nanoscale Sci & Engn, Riverside, CA 92521 USA
[4] Univ Louisville, Dept Chem, Louisville, KY 40292 USA
[5] Univ Western Ontario, Dept Earth Sci, London, ON N6A 5B7, Canada
关键词
D O I
10.1021/ja055122b
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A synthetic sequence to salts of N-alkylated pyridine-bridged 1,2,3-thiaselenazolo-1,2,3-thiaselenazolylium cations [2](+) (R-1 = Me, Et; R-2 = H) is described. The corresponding radicals 2 (R-1 = Me, Et; R-2 = H) can be generated from the cations by chemical or electrochemical reduction. Crystals of the two radicals are isostructural and consist of interpenetrating pi-stacked arrays of closed-shell Se-Se sigma-bonded dimers [2](2) laced together with numerous short intermolecular Se---Se, Se---S, and Se---N contacts. Variable-temperature magnetic, conductivity, and near-infrared optical measurements indicate that the bulk materials behave as small band gap semiconductors with room-temperature conductivities sigma(RT) near 10(-6) S cm(-1) and thermal activation energies E-a of 0.32 eV (R-1 = Me) and 0.36 eV (R-1 = Et). LMTO band structure calculations on both compounds are consistent with this interpretation. The application of external pressure leads to dramatic increases in conductivity; at 4 GPa sigma(RT) reaches a value near 10(-1) S cm(-1) for R-a = Me and 10(-2) S/cm for R-1 = Et. The conductivity remains activated for both compounds, but for R-1 = Me the activation energy E-a is reduced to near 0.03 eV at 5 GPa, suggestive of a weakly metallic state.
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收藏
页码:18159 / 18170
页数:12
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