Charge-Transfer Complexes of 4-Phenyl-1,2,3,5-dithiadiazolyl and 4-Phenyl-1,2,3,5-diselenadiazolyl with Iodine. Preparation and Solid-State Characterization of [PhCN2E2]3[I3] (E = S, Se) and [PhCN2S2][I3]

C. D. Bryan, A. W. Cordes, R. C. Haddon, R. G. Hicks, R. T. Oakley, T. T.M. Palstra, A. S. Perel, S. R. Scott

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Abstract

The 1:1 reaction of the heterocyclic radicals [PhCN2E2]· (E = S, Se) and iodine affords the mixed valence salts [PhCN2E2]3[I3], while reaction of PhCN2S2 with an excess of iodine affords the simple salt [PhCN2S2] [I3]; the solid-state structures of these complexes have been determined by X-ray crystallography. Crystals of both of the mixed valence compounds belong to the triclinic space group P1; for E =S, α = 10.278(4), b = 11.508(2), c = 13.333(4) Å, α = 114.97(2), β = 99.21 (3), γ=92.65(2)°, FW = 308.15, Z = 6; for E = Se, a = 10.368(6), b = 10.818(8), c = 13.421(8) Å, α = 80.64(5), β = 81.20(5), γ = 75.18(6)°, FW = 401.95, Z = 6. Crystals of the simple salt belong to the monoclinic space group P21/a;a = 7.366(4), b = 11.734(1), c = 15.166(2) Å,β = 95.92(3) °, FW = 1303.99(7), Z = 4. In each of the mixed valence compounds the molecular (asymmetric) unit consists of a trimeric [PhCN2E2]3+ cation and an associated triiodide anion. Within the cations the mean interannular E-E contacts are 3.181/3.377 Å (E = S/Se). The packing patterns of the two compounds show important differences. For E = S the crystal structure does not exhibit stacking of the trimeric molecular building blocks, but for E = Se the trimer units form dovetailed stacks in which consecutive layers are oriented in a transantipodal fashion. This arrangement introduces close interannular contacts between the blocks along the stack, as well as close lateral contacts. The asymmetric unit of [PhCN2S2] [I3] consists of a single PhCN2S2+ cation and an associated triiodide anion; there are no unusual stacking features. The magnetic and conductivity properties of [PhCN2Se2]3[I3] are reported, and the results discussed in the light of extended Hückel band structure calculations.

Original languageEnglish
Pages (from-to)508-515
Number of pages8
JournalChemistry of materials
Volume6
Issue number4
DOIs
Publication statusPublished - 1 Apr 1994
Externally publishedYes

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Iodine
Cations
Charge transfer
Salts
Positive ions
Anions
Negative ions
Crystals
X ray crystallography
Band structure
Crystal structure

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@article{e9794b6863b04943a1a90ffc6f1a719a,
title = "Charge-Transfer Complexes of 4-Phenyl-1,2,3,5-dithiadiazolyl and 4-Phenyl-1,2,3,5-diselenadiazolyl with Iodine. Preparation and Solid-State Characterization of [PhCN2E2]3[I3] (E = S, Se) and [PhCN2S2][I3]",
abstract = "The 1:1 reaction of the heterocyclic radicals [PhCN2E2]· (E = S, Se) and iodine affords the mixed valence salts [PhCN2E2]3[I3], while reaction of PhCN2S2 with an excess of iodine affords the simple salt [PhCN2S2] [I3]; the solid-state structures of these complexes have been determined by X-ray crystallography. Crystals of both of the mixed valence compounds belong to the triclinic space group P1; for E =S, α = 10.278(4), b = 11.508(2), c = 13.333(4) {\AA}, α = 114.97(2), β = 99.21 (3), γ=92.65(2)°, FW = 308.15, Z = 6; for E = Se, a = 10.368(6), b = 10.818(8), c = 13.421(8) {\AA}, α = 80.64(5), β = 81.20(5), γ = 75.18(6)°, FW = 401.95, Z = 6. Crystals of the simple salt belong to the monoclinic space group P21/a;a = 7.366(4), b = 11.734(1), c = 15.166(2) {\AA},β = 95.92(3) °, FW = 1303.99(7), Z = 4. In each of the mixed valence compounds the molecular (asymmetric) unit consists of a trimeric [PhCN2E2]3+ cation and an associated triiodide anion. Within the cations the mean interannular E-E contacts are 3.181/3.377 {\AA} (E = S/Se). The packing patterns of the two compounds show important differences. For E = S the crystal structure does not exhibit stacking of the trimeric molecular building blocks, but for E = Se the trimer units form dovetailed stacks in which consecutive layers are oriented in a transantipodal fashion. This arrangement introduces close interannular contacts between the blocks along the stack, as well as close lateral contacts. The asymmetric unit of [PhCN2S2] [I3] consists of a single PhCN2S2+ cation and an associated triiodide anion; there are no unusual stacking features. The magnetic and conductivity properties of [PhCN2Se2]3[I3] are reported, and the results discussed in the light of extended H{\"u}ckel band structure calculations.",
author = "Bryan, {C. D.} and Cordes, {A. W.} and Haddon, {R. C.} and Hicks, {R. G.} and Oakley, {R. T.} and Palstra, {T. T.M.} and Perel, {A. S.} and Scott, {S. R.}",
year = "1994",
month = "4",
day = "1",
doi = "10.1021/cm00040a028",
language = "English",
volume = "6",
pages = "508--515",
journal = "Chemistry of materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "4",

}

Charge-Transfer Complexes of 4-Phenyl-1,2,3,5-dithiadiazolyl and 4-Phenyl-1,2,3,5-diselenadiazolyl with Iodine. Preparation and Solid-State Characterization of [PhCN2E2]3[I3] (E = S, Se) and [PhCN2S2][I3]. / Bryan, C. D.; Cordes, A. W.; Haddon, R. C.; Hicks, R. G.; Oakley, R. T.; Palstra, T. T.M.; Perel, A. S.; Scott, S. R.

In: Chemistry of materials, Vol. 6, No. 4, 01.04.1994, p. 508-515.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Charge-Transfer Complexes of 4-Phenyl-1,2,3,5-dithiadiazolyl and 4-Phenyl-1,2,3,5-diselenadiazolyl with Iodine. Preparation and Solid-State Characterization of [PhCN2E2]3[I3] (E = S, Se) and [PhCN2S2][I3]

AU - Bryan, C. D.

AU - Cordes, A. W.

AU - Haddon, R. C.

AU - Hicks, R. G.

AU - Oakley, R. T.

AU - Palstra, T. T.M.

AU - Perel, A. S.

AU - Scott, S. R.

PY - 1994/4/1

Y1 - 1994/4/1

N2 - The 1:1 reaction of the heterocyclic radicals [PhCN2E2]· (E = S, Se) and iodine affords the mixed valence salts [PhCN2E2]3[I3], while reaction of PhCN2S2 with an excess of iodine affords the simple salt [PhCN2S2] [I3]; the solid-state structures of these complexes have been determined by X-ray crystallography. Crystals of both of the mixed valence compounds belong to the triclinic space group P1; for E =S, α = 10.278(4), b = 11.508(2), c = 13.333(4) Å, α = 114.97(2), β = 99.21 (3), γ=92.65(2)°, FW = 308.15, Z = 6; for E = Se, a = 10.368(6), b = 10.818(8), c = 13.421(8) Å, α = 80.64(5), β = 81.20(5), γ = 75.18(6)°, FW = 401.95, Z = 6. Crystals of the simple salt belong to the monoclinic space group P21/a;a = 7.366(4), b = 11.734(1), c = 15.166(2) Å,β = 95.92(3) °, FW = 1303.99(7), Z = 4. In each of the mixed valence compounds the molecular (asymmetric) unit consists of a trimeric [PhCN2E2]3+ cation and an associated triiodide anion. Within the cations the mean interannular E-E contacts are 3.181/3.377 Å (E = S/Se). The packing patterns of the two compounds show important differences. For E = S the crystal structure does not exhibit stacking of the trimeric molecular building blocks, but for E = Se the trimer units form dovetailed stacks in which consecutive layers are oriented in a transantipodal fashion. This arrangement introduces close interannular contacts between the blocks along the stack, as well as close lateral contacts. The asymmetric unit of [PhCN2S2] [I3] consists of a single PhCN2S2+ cation and an associated triiodide anion; there are no unusual stacking features. The magnetic and conductivity properties of [PhCN2Se2]3[I3] are reported, and the results discussed in the light of extended Hückel band structure calculations.

AB - The 1:1 reaction of the heterocyclic radicals [PhCN2E2]· (E = S, Se) and iodine affords the mixed valence salts [PhCN2E2]3[I3], while reaction of PhCN2S2 with an excess of iodine affords the simple salt [PhCN2S2] [I3]; the solid-state structures of these complexes have been determined by X-ray crystallography. Crystals of both of the mixed valence compounds belong to the triclinic space group P1; for E =S, α = 10.278(4), b = 11.508(2), c = 13.333(4) Å, α = 114.97(2), β = 99.21 (3), γ=92.65(2)°, FW = 308.15, Z = 6; for E = Se, a = 10.368(6), b = 10.818(8), c = 13.421(8) Å, α = 80.64(5), β = 81.20(5), γ = 75.18(6)°, FW = 401.95, Z = 6. Crystals of the simple salt belong to the monoclinic space group P21/a;a = 7.366(4), b = 11.734(1), c = 15.166(2) Å,β = 95.92(3) °, FW = 1303.99(7), Z = 4. In each of the mixed valence compounds the molecular (asymmetric) unit consists of a trimeric [PhCN2E2]3+ cation and an associated triiodide anion. Within the cations the mean interannular E-E contacts are 3.181/3.377 Å (E = S/Se). The packing patterns of the two compounds show important differences. For E = S the crystal structure does not exhibit stacking of the trimeric molecular building blocks, but for E = Se the trimer units form dovetailed stacks in which consecutive layers are oriented in a transantipodal fashion. This arrangement introduces close interannular contacts between the blocks along the stack, as well as close lateral contacts. The asymmetric unit of [PhCN2S2] [I3] consists of a single PhCN2S2+ cation and an associated triiodide anion; there are no unusual stacking features. The magnetic and conductivity properties of [PhCN2Se2]3[I3] are reported, and the results discussed in the light of extended Hückel band structure calculations.

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