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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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
StatePublished - 1 Feb 1994

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Iodine
Dimers
Charge transfer
Salts
Sublimation
Crystal structure
Crystals
Magnetic susceptibility
Temperature
Single crystals
Atoms
Chemical analysis

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Bryan, C. D. ; Cordes, A. W. ; Haddon, R. C. ; Palstra, T. T.M. ; Perel, A. S. ; Schneemeyer, L. F. ; Waszczak, J. V. ; Hicks, R. G. ; Kennepohl, D. K. ; MacKinnon, C. D. ; Oakley, R. T. ; Scott, S. R. / Molecular Conductors from Neutral-Radical Charge-Transfer Salts : Ppreparation and Characterization of an I Doped Hexagonal Phase of 1, 2, 3, 5-dithiadiazolyl ([HCN2S2].). In: Journal of the American Chemical Society. 1994 ; Vol. 116, No. 4. pp. 1205-1210.
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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) {\AA}, 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) {\AA}, 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.",
author = "Bryan, {C. D.} and Cordes, {A. W.} and Haddon, {R. C.} and Palstra, {T. T.M.} and Perel, {A. S.} and Schneemeyer, {L. F.} and Waszczak, {J. V.} and Hicks, {R. G.} and Kennepohl, {D. K.} and MacKinnon, {C. D.} and Oakley, {R. T.} and Scott, {S. R.}",
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Bryan, CD, Cordes, AW, Haddon, RC, Palstra, TTM, Perel, AS, Schneemeyer, LF, Waszczak, JV, Hicks, RG, Kennepohl, DK, MacKinnon, CD, Oakley, RT & Scott, SR 1994, 'Molecular Conductors from Neutral-Radical Charge-Transfer Salts: Ppreparation and Characterization of an I Doped Hexagonal Phase of 1, 2, 3, 5-dithiadiazolyl ([HCN2S2].)', Journal of the American Chemical Society, vol. 116, no. 4, pp. 1205-1210. https://doi.org/10.1021/ja00083a005

Molecular Conductors from Neutral-Radical Charge-Transfer Salts : Ppreparation and Characterization of an I Doped Hexagonal Phase of 1, 2, 3, 5-dithiadiazolyl ([HCN2S2].). / Bryan, C. D.; Cordes, A. W.; Haddon, R. C.; Palstra, T. T.M.; Perel, A. S.; Schneemeyer, L. F.; Waszczak, J. V.; Hicks, R. G.; Kennepohl, D. K.; MacKinnon, C. D.; Oakley, R. T.; Scott, S. R.

In: Journal of the American Chemical Society, Vol. 116, No. 4, 01.02.1994, p. 1205-1210.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Molecular Conductors from Neutral-Radical Charge-Transfer Salts

T2 - Ppreparation and Characterization of an I Doped Hexagonal Phase of 1, 2, 3, 5-dithiadiazolyl ([HCN2S2].)

AU - Bryan, C. D.

AU - Cordes, A. W.

AU - Haddon, R. C.

AU - Palstra, T. T.M.

AU - Perel, A. S.

AU - Schneemeyer, L. F.

AU - Waszczak, J. V.

AU - Hicks, R. G.

AU - Kennepohl, D. K.

AU - MacKinnon, C. D.

AU - Oakley, R. T.

AU - Scott, S. R.

PY - 1994/2/1

Y1 - 1994/2/1

N2 - 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.

AB - 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.

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