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Volumn 4, Issue 8, 1998, Pages 1509-1522

Redox states of long oligothiophenes: Two polarons on a single chain

Author keywords

Conducting materials; Oligomers; Pi interactions; Radical ions; Redox chemistry

Indexed keywords


EID: 0031877896     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3765(19980807)4:8<1509::aid-chem1509>3.0.co;2-%23     Document Type: Article
Times cited : (255)

References (86)
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    • note
    • In chemical terminology a positive polaron (which is an expression used in solid-state physics) corresponds to a radical cation, associated to a local geometry relaxation; see ref. [6].
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    • A bipolarom is a pair of like charges with an associated strong local geometry deformation; see ref. [6].
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    • Furukawa (ref. [9]) has estimated the expected intensity ratio of the two subgap absorptions for polythiophene based on FBC theory (ref. [5]) to be about 14, in sharp contrast with the observed ratio of about 1.2.
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    • Detailed investigations of the influence of the solvent and solvent polarity on the dimerization enthalpy of radical cations are in progress.
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    • note
    • It is also possible to rationalize this by stating that the energy required to remove an electron from a fragment of a long chain which already carries a charge is higher than the energy needed to remove the electron from a neutral part of the same chain.
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    • note
    • 2, respectively.
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    • Examples can be found for oligothiophenes in ref. [13], for oligopyrroles in ref. [25], and for oligo(p-phenylene vinylene)s see: M. Deusen, H. Bässler, Chem. Phys. 1992, 164, 247.
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    • Here we define a diradical a molecule as one in which two electrons occupy two degenerate or nearly degenerate molecular orbitals. Angew. Chem. 1972, 84, 86; L. Salem, C. Rowland, Angew. Chem. Int. Ed. Engl. 1972, 11, 92.
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    • Here we define a diradical a molecule as one in which two electrons occupy two degenerate or nearly degenerate molecular orbitals. Angew. Chem. 1972, 84, 86; L. Salem, C. Rowland, Angew. Chem. Int. Ed. Engl. 1972, 11, 92.
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    • note
    • B 〉 ) ≠ 0.
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    • Small amounts of α-chlorinated by-products are known to be formed during the oligomer synthesis in the oxidative coupling reaction of the α-lithio derivatives with cupric chloride. See: a) H. E. Katz, L. Torsi, A. Dodabalapur, Chem. Mater. 1995, 7, 2235; b) H. E. Katz, L. Torsi, A. Dodabalapur, A. J. Lovinger, R. Ruel, Polym. Mater. Sci. Eng. 1995, 72, 467.
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    • Small amounts of α-chlorinated by-products are known to be formed during the oligomer synthesis in the oxidative coupling reaction of the α-lithio derivatives with cupric chloride. See: a) H. E. Katz, L. Torsi, A. Dodabalapur, Chem. Mater. 1995, 7, 2235; b) H. E. Katz, L. Torsi, A. Dodabalapur, A. J. Lovinger, R. Ruel, Polym. Mater. Sci. Eng. 1995, 72, 467.
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    • Katz, H.E.1    Torsi, L.2    Dodabalapur, A.3    Lovinger, A.J.4    Ruel, R.5
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    • .+ is expected at m/z = 1658.6 amu, i.e. 2 amu less than observed.
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    • note
    • 2+ π dimer, while the band at E = 1.81 eV evolves into a shoulder.
  • 67
    • 85080553153 scopus 로고    scopus 로고
    • note
    • The exact origin of this discrepancy is unclear. The only difference between the two experiments is that Bäuerle et al.[17] used one regioisomer of 6T (i.e., 3″″,4′-didodecyl-2,2′:5′,2″:5″, 2‴: 5‴,2″″:5‴,2″‴-sexithiophene) while in this study the dodecyl side chains on the second and fifth thiophene ring are either at the 3 or the 4 position, resulting in a mixture of three regioisomers, (3′,4″″)-, (3′,3″″)-, and (3″″,4′)-dodecyl, for 6T.
  • 69
    • 85080605570 scopus 로고    scopus 로고
    • note
    • 2 + 1.86/n + 2.49 eV is obtained for the absorption maximum of neutral nT, which gives n ≈ 31 when E = 2.56eV.
  • 73
    • 85080468625 scopus 로고    scopus 로고
    • note
    • AB of the two singly occupied MOs carrying the unpaired electrons.
  • 75
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    • note
    • -7 eV) to still give the diradical spectrum. Clearly this is much less than the thermal energy.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.