Conducting charge-transfer salts based on neutral π-radicals

C. D. Bryan, A. W. Cordes, R. M. Fleming, N. A. George, S. H. Glarum, R. C. Haddon, R. T. Oakley, T. T.M. Palstra, A. S. Perel, L. F. Schneemeyer, J. V. Waszczak

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Abstract

MOST molecular conductors rely on charge transfer to create carriers. For example, the ET salts1 are hole-doped whereas the C60 salts2 are electron-doped. Neutral radical species in which bands are formed by π-orbital overlap would be expected to have half-filled bands and thus to be conducting3, but no such metals have yet been reported. Here we report the synthesis and characterization of a molecular conductor which combines both of these approaches: energy bands are formed from one-dimensional stacks of neutral π-radicals, and the material is rendered conducting by electron transfer from the conduction band following doping with an acceptor. The radical species is the l,4-phenylene-bis(dithiadiazolyl) diradical 1,4-[(S2N2C)C6H4(CN 2S2)] (2 in Fig. 1), reaction of which with iodine vapour leads to crystals of [2][I]. At low temperatures this compound is essentially a diamagnetic insulator, but above 200 K the conductivity and magnetic susceptibility increase markedly, and at room temperature the conductivity reaches l00 S cm-1, which is comparable to that shown by conventional molecular charge-transfer salts.

Original languageEnglish
Pages (from-to)821-823
Number of pages3
JournalNature
Volume365
Issue number6449
DOIs
StatePublished - 1 Jan 1993

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Charge transfer
Salts
Electrons
Conduction bands
Magnetic susceptibility
Iodine
Band structure
Metals
Vapors
Doping (additives)
Temperature
Crystals

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Bryan, C. D., Cordes, A. W., Fleming, R. M., George, N. A., Glarum, S. H., Haddon, R. C., ... Waszczak, J. V. (1993). Conducting charge-transfer salts based on neutral π-radicals. Nature, 365(6449), 821-823. https://doi.org/10.1038/365821a0
Bryan, C. D. ; Cordes, A. W. ; Fleming, R. M. ; George, N. A. ; Glarum, S. H. ; Haddon, R. C. ; Oakley, R. T. ; Palstra, T. T.M. ; Perel, A. S. ; Schneemeyer, L. F. ; Waszczak, J. V. / Conducting charge-transfer salts based on neutral π-radicals. In: Nature. 1993 ; Vol. 365, No. 6449. pp. 821-823.
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Bryan, CD, Cordes, AW, Fleming, RM, George, NA, Glarum, SH, Haddon, RC, Oakley, RT, Palstra, TTM, Perel, AS, Schneemeyer, LF & Waszczak, JV 1993, 'Conducting charge-transfer salts based on neutral π-radicals', Nature, vol. 365, no. 6449, pp. 821-823. https://doi.org/10.1038/365821a0

Conducting charge-transfer salts based on neutral π-radicals. / Bryan, C. D.; Cordes, A. W.; Fleming, R. M.; George, N. A.; Glarum, S. H.; Haddon, R. C.; Oakley, R. T.; Palstra, T. T.M.; Perel, A. S.; Schneemeyer, L. F.; Waszczak, J. V.

In: Nature, Vol. 365, No. 6449, 01.01.1993, p. 821-823.

Research output: Contribution to journalArticle

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N2 - MOST molecular conductors rely on charge transfer to create carriers. For example, the ET salts1 are hole-doped whereas the C60 salts2 are electron-doped. Neutral radical species in which bands are formed by π-orbital overlap would be expected to have half-filled bands and thus to be conducting3, but no such metals have yet been reported. Here we report the synthesis and characterization of a molecular conductor which combines both of these approaches: energy bands are formed from one-dimensional stacks of neutral π-radicals, and the material is rendered conducting by electron transfer from the conduction band following doping with an acceptor. The radical species is the l,4-phenylene-bis(dithiadiazolyl) diradical 1,4-[(S2N2C)C6H4(CN 2S2)] (2 in Fig. 1), reaction of which with iodine vapour leads to crystals of [2][I]. At low temperatures this compound is essentially a diamagnetic insulator, but above 200 K the conductivity and magnetic susceptibility increase markedly, and at room temperature the conductivity reaches l00 S cm-1, which is comparable to that shown by conventional molecular charge-transfer salts.

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Bryan CD, Cordes AW, Fleming RM, George NA, Glarum SH, Haddon RC et al. Conducting charge-transfer salts based on neutral π-radicals. Nature. 1993 Jan 1;365(6449):821-823. https://doi.org/10.1038/365821a0