메뉴 건너뛰기




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 : (258)

References (86)
  • 4
    • 25044457789 scopus 로고
    • W. P. Su, J. R. Schrieffer, A. J. Heeger, Phys. Rev. Lett. 1979, 42, 1698; Phys. Rev. B 1980, 22, 2099.
    • (1980) Phys. Rev. B , vol.22 , pp. 2099
  • 11
    • 85080602475 scopus 로고    scopus 로고
    • 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].
  • 12
    • 85080597947 scopus 로고    scopus 로고
    • note
    • A bipolarom is a pair of like charges with an associated strong local geometry deformation; see ref. [6].
  • 13
    • 85080543038 scopus 로고    scopus 로고
    • note
    • 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.
  • 23
    • 84886039069 scopus 로고
    • P. Bäuerle, U. Segelbacher, K.-U. Gaudl, D. Huttenlocher, M. Mehring, Angew. Chem. 1993, 105, 125; Angew. Chem. Int. Ed. Engl. 1993, 32, 76.
    • (1993) Angew. Chem. Int. Ed. Engl. , vol.32 , pp. 76
  • 30
    • 85080493166 scopus 로고    scopus 로고
    • note
    • Detailed investigations of the influence of the solvent and solvent polarity on the dimerization enthalpy of radical cations are in progress.
  • 33
    • 33748226344 scopus 로고    scopus 로고
    • J. A. E. H. van Haare, L. Groenendaal, E. E. Havinga, R. A. J. Janssen, E. W. Meijer, Angew. Chem. 1996, 108, 696; Angew. Chem. Int. Ed. Engl. 1996, 35, 638.
    • (1996) Angew. Chem. Int. Ed. Engl. , vol.35 , pp. 638
  • 37
    • 33748666734 scopus 로고
    • P. Bäuerle, T. Fisher, B. Bidlingmeier, A. Stabel, J. P. Rabe, Angew. Chem. 1995, 107, 335; Angew. Chem. Int. Ed. Engl. 1995, 34, 303.
    • (1995) Angew. Chem. Int. Ed. Engl. , vol.34 , pp. 303
  • 39
    • 85080586694 scopus 로고    scopus 로고
    • 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.
  • 43
    • 85080608448 scopus 로고    scopus 로고
    • note
    • 2, respectively.
  • 44
    • 0003113119 scopus 로고
    • 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.
    • (1992) Chem. Phys. , vol.164 , pp. 247
    • Deusen, M.1    Bässler, H.2
  • 45
    • 84901796319 scopus 로고
    • 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.
    • (1972) Angew. Chem. , vol.84 , pp. 86
  • 46
    • 84981911761 scopus 로고
    • 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.
    • (1972) Angew. Chem. Int. Ed. Engl. , vol.11 , pp. 92
    • Salem, L.1    Rowland, C.2
  • 47
    • 0002366798 scopus 로고
    • Ed.: W. T. Borden, John Wiley, New York
    • W. T. Borden in Diradicals (Ed.: W. T. Borden), John Wiley, New York, 1982, pp. 1-72.
    • (1982) Diradicals , pp. 1-72
    • Borden, W.T.1
  • 48
    • 0003468774 scopus 로고
    • McGraw-Hill, New York
    • -, are given by the following equations (see: A. Szabo, N. S. Ostlund, Modern Quantum Chemistry, McGraw-Hill, New York, 1989): chemical equation presented.
    • (1989) Modern Quantum Chemistry
    • Szabo, A.1    Ostlund, N.S.2
  • 49
    • 85080581164 scopus 로고    scopus 로고
    • note
    • B 〉 ) ≠ 0.
  • 59
    • 33751155255 scopus 로고
    • 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.
    • (1995) Chem. Mater. , vol.7 , pp. 2235
    • Katz, H.E.1    Torsi, L.2    Dodabalapur, A.3
  • 60
    • 33751155255 scopus 로고
    • 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.
    • (1995) Polym. Mater. Sci. Eng. , vol.72 , pp. 467
    • Katz, H.E.1    Torsi, L.2    Dodabalapur, A.3    Lovinger, A.J.4    Ruel, R.5
  • 61
    • 85080496248 scopus 로고    scopus 로고
    • note
    • .+ is expected at m/z = 1658.6 amu, i.e. 2 amu less than observed.
  • 66
    • 85080526151 scopus 로고    scopus 로고
    • 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
    • 85080605637 scopus 로고    scopus 로고
    • note
    • -7 eV) to still give the diradical spectrum. Clearly this is much less than the thermal energy.
  • 79
    • 33748222143 scopus 로고
    • c) M. Dvolaitzky, R. Chirarelli, A. Rassat, Angew. Chem. 1992, 104, 220; Angew. Chem. Int. Ed. Engl. 1992, 31, 180;
    • (1992) Angew. Chem. Int. Ed. Engl. , vol.31 , pp. 180


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.