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Volumn 129, Issue 4, 2007, Pages 828-838

Molecular and electronic structures of the long-bonded π-dimers of tetrathiafulvalene cation-radical in intermolecular electron transfer and in (solid-state) conductivity

Author keywords

[No Author keywords available]

Indexed keywords

INTERMOLECULAR ELECTRON TRANSFER; MOLECULAR ORBITAL ANALYSIS; MULLIKEN HUSH ANALYSIS;

EID: 33846622957     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja064166x     Document Type: Article
Times cited : (157)

References (114)
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    • (a) TTF Chemistry: Fundamentals and Applications of Tetrathiafulvalene; Yamada, J.-I., Sugimoto, T., Eds.; Kodansha Springer: Berlin, 2004.
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    • See also: Batail, P. Guest Ed., Molecular Conductors Thematic Issue. Chem. Rev. 2004, 104 (11).
    • (f) See also: Batail, P. Guest Ed., Molecular Conductors Thematic Issue. Chem. Rev. 2004, 104 (11).
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    • However, for a recent discussion of the validity of this relationship based on the study of somewhat related bridged mixed-valence systems, see: Nelsen, S. F.; Luo, Y.; Weaver, M. N.; Lockard, J. V.; Zink, J. F. J. Org. Chem. 2006, 71, 4286.
    • However, for a recent discussion of the validity of this relationship based on the study of somewhat related bridged mixed-valence systems, see: Nelsen, S. F.; Luo, Y.; Weaver, M. N.; Lockard, J. V.; Zink, J. F. J. Org. Chem. 2006, 71, 4286.
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    • -.), in which the mixed-valence dyads represent p-doping and n-doping, respectively, of stacked arrays.
    • -.), in which the mixed-valence dyads represent p-doping and n-doping, respectively, of stacked arrays.
  • 45
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    • 13,14a,18 Therefore, to maintain historical integrity, the notations CT and IV are hereinafter referred to interchangeably.
    • 13,14a,18 Therefore, to maintain historical integrity, the notations CT and IV are hereinafter referred to interchangeably.
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    • Devreese, J. T, Evrard, R. P, van Doren, V. E, Eds, Plenum Press: New York
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    • Heger, A.J.1
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    • ., see: King, B. T.; Noll, B. C.; McKinley, A. J.; Michl, J. J. Am. Chem. Soc. 1996, 118, 10902.
    • ., see: King, B. T.; Noll, B. C.; McKinley, A. J.; Michl, J. J. Am. Chem. Soc. 1996, 118, 10902.
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    • 29c-e
    • 29c-e
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    • For other systems with partial charge-transfer, see: c
    • For other systems with partial charge-transfer, see: (c) Umland, T. C.; Allie, S.; Kuhlmann, T.; Coppens, P. J. Phys. Chem. 1988, 92, 6456.
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    • D, of the dimer shows consistent but slight blue shifts upon lowering the temperature, which we tentatively ascribe to the labile nature of such long-bonded dimeric species (vide supra).
    • D, of the dimer shows consistent but slight blue shifts upon lowering the temperature, which we tentatively ascribe to the labile nature of such long-bonded dimeric species (vide supra).
  • 78
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    • Compare: Lu, J.-M; Rosokha, S. V.; Kochi, J. K. J. Am. Chem. Soc. 2003, 125, 12161.
    • Compare: Lu, J.-M; Rosokha, S. V.; Kochi, J. K. J. Am. Chem. Soc. 2003, 125, 12161.
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    • Note that direct comparison in the less polar dichloromethane was not possible, owing to the low solubility of the perchlorate salt
    • (b) Note that direct comparison in the less polar dichloromethane was not possible, owing to the low solubility of the perchlorate salt.
  • 81
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    • +. in solutions (see Figure S12).
    • +. in solutions (see Figure S12).
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    • 1970, 66, 2939.
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    • π = 3.5 ± 0.2 Å.
    • π = 3.5 ± 0.2 Å.
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    • However, the stacking structures fall essentially into two general classes, viz., the vertical and slipped dyads exemplified by structures A and B, respectively, in Chart 2. Furthermore, B stacks show variable displacements from the vertical of up to 1.5-2.0 Å.
    • (b) However, the stacking structures fall essentially into two general classes, viz., the vertical and slipped dyads exemplified by structures A and B, respectively, in Chart 2. Furthermore, B stacks show variable displacements from the vertical of up to 1.5-2.0 Å.
  • 93
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    • The crossed TTF dyad at the same interplanar separation represents the rather unique exception. See: Triki, S.; Ouahab, L.; Halet, J. F.; Pena, O.; Padiou, J.; Grandjean, D.; Garrigou-Lagrange, C.; Delhaes, P. J. Chem. Soc., Dalton Trans. 1992, 1217.
    • (c) The crossed TTF dyad at the same interplanar separation represents the rather unique exception. See: Triki, S.; Ouahab, L.; Halet, J. F.; Pena, O.; Padiou, J.; Grandjean, D.; Garrigou-Lagrange, C.; Delhaes, P. J. Chem. Soc., Dalton Trans. 1992, 1217.
  • 94
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    • Note, however, the labile nature of the dimer in solution, as discussed in section 3.3
    • (a) Note, however, the labile nature of the dimer in solution, as discussed in section 3.3.
  • 95
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    • For ab initio computations of the unique bonding extant in long-bonded π-dimers, see refs 17b, 33a, and 35
    • (b) For ab initio computations of the unique bonding extant in long-bonded π-dimers, see refs 17b, 33a, and 35.
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    • As noted recently,43b the solvent dependence of the intervalence band for, number
    • s) and the Guttman donor number.
    • s) and the Guttman donor
    • Class1
  • 102
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    • -1 in tetrahydrofuran solutions.
    • -1 in tetrahydrofuran solutions.
  • 103
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    • a represents a composite of the electrontransfer barrier, the thermodynamics of the precursor complex, and the temperature dependence of the diffusion rate constant.
    • a represents a composite of the electrontransfer barrier, the thermodynamics of the precursor complex, and the temperature dependence of the diffusion rate constant.
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    • Pople, J. A.; et al. Gaussian 98, Revision A. 11.3; Gaussian, Inc.: Pittsburgh, PA, 1998.
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    • -1 for the dyad with the interplanar separation of 3.5 Å and the lateral shift of 1.5 Å.
    • -1 for the dyad with the interplanar separation of 3.5 Å and the lateral shift of 1.5 Å.
  • 110
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    • However, the curves in Figure 5B,C (Hab vs d∥ or d⊥) show additional local maxima, similar to those reported for some other long-bonded π-dyads.4,10 Such dependences result from the complex nodal shape of the tetrathiafulvalene HOMO (see Chart S1 in the Supporting Information, since its symmetry simultaneously favors bonding interaction for (i) the vertical structure A, ii) certain relative (parallel or perpendicular) displacements B in Chart 2, and, in addition, iii) the perpendicularly crossed structure,39c such that structural changes occurring within the TTF plane are (more or less) equally accessible. This orbital (symmetry) situation differs from that of some other systems, such as TCNE/TCNE, see refs 10, 17, and 33a
    • -. (see refs 10, 17, and 33a).
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    • Sheldrick, G. M. SADABS, Version 2.03; Bruker/Siemens Area Detector Absorption and Other Corrections, 2000
    • (a) Sheldrick, G. M. SADABS, Version 2.03; Bruker/Siemens Area Detector Absorption and Other Corrections, 2000.


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