Functionalised oligoenes with unusual topologies: Synthesis, electrochemistry and structural studies on redox-active [3]- and [4]-dendralenes

M.R. Bryce, M.A. Coffin, P.J. Skabara, A.J. Moore, A.S. Batsanov, J.A.K. Howard

Research output: Contribution to journalArticle

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Abstract

New [3]- and [4]-dendralenes bearing electron-donor 1,3-dithiole and ferrocene substituents have been synthesised. Compounds 8, 15 and 17 have been characterised by single-crystal X-ray diffraction. Two of the dithiole rings of 8 are conjugated (dihedral angle 9 degrees), while the third dithiole ring is almost orthogonal to this plane, and hence its pi-electron system is isolated. For the dendralene precursor molecule 15, the substituted cyclopentadienyl ring, two C=C bonds and fused dithiole and dithiine rings comprise an extended pi-conjugated system. In molecule 17 the potential conjugation path C(6)C(3) C(4)C(5)-C5H5 is distorted by an 8 degrees twist around the C(3)-C(4) bond and a 7 degrees twist around the C(5)-C(21) bond, and the delocalisation along the chain is insignificant. Solution electrochemical data demonstrate that the dendralenes are strong pi-electron donors, which give rise to dication, radical trication or tetracation species. Spectroelectrochemical studies on compounds 7 and 10 suggest that the radical species are situated within the linear 1,2-ethylenediylidene moieties and that a conformational change may occur at the dication redox stage. UV/Vis spectroscopic data are consistent with poor cross-conjugation in these systems.
LanguageEnglish
Pages1955-1962
Number of pages7
JournalChemistry - A European Journal
Volume6
Issue number11
DOIs
Publication statusPublished - 2 Jun 2000

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Electrochemistry
Topology
Electrons
Bearings (structural)
Molecules
Dihedral angle
Single crystals
X ray diffraction
Oxidation-Reduction

Keywords

  • dendralenes
  • electrochemistry
  • ferrocene
  • radicals
  • structure elucidation

Cite this

Bryce, M.R. ; Coffin, M.A. ; Skabara, P.J. ; Moore, A.J. ; Batsanov, A.S. ; Howard, J.A.K. / Functionalised oligoenes with unusual topologies: Synthesis, electrochemistry and structural studies on redox-active [3]- and [4]-dendralenes. In: Chemistry - A European Journal. 2000 ; Vol. 6, No. 11. pp. 1955-1962.
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Functionalised oligoenes with unusual topologies: Synthesis, electrochemistry and structural studies on redox-active [3]- and [4]-dendralenes. / Bryce, M.R.; Coffin, M.A.; Skabara, P.J.; Moore, A.J.; Batsanov, A.S.; Howard, J.A.K.

In: Chemistry - A European Journal, Vol. 6, No. 11, 02.06.2000, p. 1955-1962.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Functionalised oligoenes with unusual topologies: Synthesis, electrochemistry and structural studies on redox-active [3]- and [4]-dendralenes

AU - Bryce, M.R.

AU - Coffin, M.A.

AU - Skabara, P.J.

AU - Moore, A.J.

AU - Batsanov, A.S.

AU - Howard, J.A.K.

PY - 2000/6/2

Y1 - 2000/6/2

N2 - New [3]- and [4]-dendralenes bearing electron-donor 1,3-dithiole and ferrocene substituents have been synthesised. Compounds 8, 15 and 17 have been characterised by single-crystal X-ray diffraction. Two of the dithiole rings of 8 are conjugated (dihedral angle 9 degrees), while the third dithiole ring is almost orthogonal to this plane, and hence its pi-electron system is isolated. For the dendralene precursor molecule 15, the substituted cyclopentadienyl ring, two C=C bonds and fused dithiole and dithiine rings comprise an extended pi-conjugated system. In molecule 17 the potential conjugation path C(6)C(3) C(4)C(5)-C5H5 is distorted by an 8 degrees twist around the C(3)-C(4) bond and a 7 degrees twist around the C(5)-C(21) bond, and the delocalisation along the chain is insignificant. Solution electrochemical data demonstrate that the dendralenes are strong pi-electron donors, which give rise to dication, radical trication or tetracation species. Spectroelectrochemical studies on compounds 7 and 10 suggest that the radical species are situated within the linear 1,2-ethylenediylidene moieties and that a conformational change may occur at the dication redox stage. UV/Vis spectroscopic data are consistent with poor cross-conjugation in these systems.

AB - New [3]- and [4]-dendralenes bearing electron-donor 1,3-dithiole and ferrocene substituents have been synthesised. Compounds 8, 15 and 17 have been characterised by single-crystal X-ray diffraction. Two of the dithiole rings of 8 are conjugated (dihedral angle 9 degrees), while the third dithiole ring is almost orthogonal to this plane, and hence its pi-electron system is isolated. For the dendralene precursor molecule 15, the substituted cyclopentadienyl ring, two C=C bonds and fused dithiole and dithiine rings comprise an extended pi-conjugated system. In molecule 17 the potential conjugation path C(6)C(3) C(4)C(5)-C5H5 is distorted by an 8 degrees twist around the C(3)-C(4) bond and a 7 degrees twist around the C(5)-C(21) bond, and the delocalisation along the chain is insignificant. Solution electrochemical data demonstrate that the dendralenes are strong pi-electron donors, which give rise to dication, radical trication or tetracation species. Spectroelectrochemical studies on compounds 7 and 10 suggest that the radical species are situated within the linear 1,2-ethylenediylidene moieties and that a conformational change may occur at the dication redox stage. UV/Vis spectroscopic data are consistent with poor cross-conjugation in these systems.

KW - dendralenes

KW - electrochemistry

KW - ferrocene

KW - radicals

KW - structure elucidation

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U2 - 10.1002/1521-3765(20000602)6:11<1955::AID-CHEM1955>3.0.CO;2-B

DO - 10.1002/1521-3765(20000602)6:11<1955::AID-CHEM1955>3.0.CO;2-B

M3 - Article

VL - 6

SP - 1955

EP - 1962

JO - Chemistry - A European Journal

T2 - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 11

ER -