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Volumn 127, Issue 8, 2005, Pages 2666-2676

Polyynes as a model for carbyne: Synthesis, physical properties, and nonlinear optical response

Author keywords

[No Author keywords available]

Indexed keywords

ACETYLENE; AROMATIC HYDROCARBONS; CRYSTALLOGRAPHY; DERIVATIVES; DIFFERENTIAL SCANNING CALORIMETRY; NONLINEAR OPTICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLARIZATION; ULTRAVIOLET SPECTROSCOPY;

EID: 14744270102     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja044526l     Document Type: Article
Times cited : (368)

References (104)
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    • (b) Cataldo, F. Carbon 2004, 42, 129-142.
    • (2004) Carbon , vol.42 , pp. 129-142
    • Cataldo, F.1
  • 22
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    • Wiley-VCH: Weinheim, Germany, Chapter 8
    • For an excellent review of this earlier work, see: Hopf, H. Classics in Hydrocarbon Synthesis; Wiley-VCH: Weinheim, Germany, 2000; Chapter 8.
    • (2000) Classics in Hydrocarbon Synthesis
    • Hopf, H.1
  • 57
    • 14744267248 scopus 로고    scopus 로고
    • note
    • The point at which quenching was initiated was essential to the success of the rearrangement. If quenched too soon, byproducts resulting from protonation of the lithiated intermediates are formed and greatly complicate purification because of similar retention times on Chromatographic supports. TLC analysis was therefore required during the warming stage to ensure complete rearrangement. The reaction mixture was consequently allowed to warm up to ∼-5 °C to ensure complete rearrangement. See Supporting Information for complete experimental details.
  • 61
    • 0033953042 scopus 로고    scopus 로고
    • During the course of our study, Hirsch and co-workers reported a similar observation; see ref 26. To the best of our knowledge, these are the only two known examples of an apparent loss of C2 during a Hay coupling reaction. Cleavage of single bonds in polyynes has, however, been reported for other metals (e.g., Zr and Ti). See: Rosenthal, U.; Pellny, P. M.; Kirchbauer, F. G.; Burlakov, V. V. Acc. Chem. Res. 2000, 33, 119-129.
    • (2000) Acc. Chem. Res. , vol.33 , pp. 119-129
    • Rosenthal, U.1    Pellny, P.M.2    Kirchbauer, F.G.3    Burlakov, V.V.4
  • 62
    • 14744269267 scopus 로고    scopus 로고
    • note
    • DSC traces of compounds 1-7 can be found in the Supporting Information.
  • 66
    • 14744269801 scopus 로고    scopus 로고
    • note
    • For the other octayne structure, see ref 31a. For an excellent summary of the crystallographic and solid-state properties of polyynes, see ref 47. A preliminary account of the structure of hexayne 5 can be found in ref 47.
  • 67
    • 14744269119 scopus 로고    scopus 로고
    • note
    • A tabular summary of bond lengths for 3-6 is provided in the Supporting Information.
  • 68
    • 14744271319 scopus 로고    scopus 로고
    • note
    • See Supporting Information for details and discussion.
  • 69
    • 2342530482 scopus 로고    scopus 로고
    • A preliminary account of these results has been reported. See: Slepkov, A. D.; Hegmann, F. A.; Eisler, S.; Elliott, E.; Tykwinski, R. R. J. Chem. Phys. 2004, 120, 6807-6810. For a discussion of the electronic properties of cross-conjugated enynes such as 12, 13, and 17. see: Zhao, Y.; McDonald, R.; Tykwinski, R. R. J. Org. Chem. 2002, 67, 2805-2812.
    • (2004) J. Chem. Phys. , vol.120 , pp. 6807-6810
    • Slepkov, A.D.1    Hegmann, F.A.2    Eisler, S.3    Elliott, E.4    Tykwinski, R.R.5
  • 70
    • 0037012815 scopus 로고    scopus 로고
    • A preliminary account of these results has been reported. See: Slepkov, A. D.; Hegmann, F. A.; Eisler, S.; Elliott, E.; Tykwinski, R. R. J. Chem. Phys. 2004, 120, 6807-6810. For a discussion of the electronic properties of cross-conjugated enynes such as 12, 13, and 17. see: Zhao, Y.; McDonald, R.; Tykwinski, R. R. J. Org. Chem. 2002, 67, 2805-2812.
    • (2002) J. Org. Chem. , vol.67 , pp. 2805-2812
    • Zhao, Y.1    McDonald, R.2    Tykwinski, R.R.3
  • 71
    • 14744279012 scopus 로고    scopus 로고
    • Müllen, K., Wegner, G., Eds.; Wiley-VCH: Weinheim, Germany, Chapter 8
    • Bubeck, C. In Electronic Materials: The Oligomer Approach; Müllen, K., Wegner, G., Eds.; Wiley-VCH: Weinheim, Germany, 1998, Chapter 8.
    • (1998) Electronic Materials: The Oligomer Approach
    • Bubeck, C.1
  • 75
    • 14744267367 scopus 로고    scopus 로고
    • note
    • 2 values).
  • 78
    • 14744270326 scopus 로고    scopus 로고
    • M. Sc. Thesis, University of Alberta, Edmonton. Alberta, Canada
    • Slepkov, A. D. M. Sc. Thesis, University of Alberta, Edmonton. Alberta, Canada, 2002.
    • (2002)
    • Slepkov, A.D.1
  • 84
    • 14744275085 scopus 로고    scopus 로고
    • note
    • Whereas there is some debate as to the interchangeability of L and n as a universal parameter, for polyynes, the two parameters scale identically.
  • 86
  • 89
    • 0030732797 scopus 로고    scopus 로고
    • With the possible exception of oligorylenes, for which a power-law behavior with an exponent of c = 5.6 was estimated. See: Rumi, M.; Zerbi, G.; Müllen, K.; Müller, G.; Rehahn, M. J. Chem. Phys. 1997, 106, 24-34.
    • (1997) J. Chem. Phys. , vol.106 , pp. 24-34
    • Rumi, M.1    Zerbi, G.2    Müllen, K.3    Müller, G.4    Rehahn, M.5
  • 95
    • 0001423135 scopus 로고
    • While the optimal geometry of an alkyne is linear, distortion can occur. For a discussion, see: Krebs, A.; Wilke, J. Top. Curr. Chem. 1983, 109, 189-233.
    • (1983) Top. Curr. Chem. , vol.109 , pp. 189-233
    • Krebs, A.1    Wilke, J.2
  • 102
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    • (c) Kuzyk, M. G. Opt. Lett. 2000, 25, 1183-1185.
    • (2000) Opt. Lett. , vol.25 , pp. 1183-1185
    • Kuzyk, M.G.1


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