Recent Progress in the Chemistry and Physics of Poly (Diacetylenes)

  • G. Wegner
Part of the Nato Conference Series book series (NATOCS, volume 1)


The search for macroscopic single crystals of polymers with the aim to study the intrinsic solid-state properties of macromolecules and their interaction in a perfect three dimensional lattice is as old as polymer science itself. Unfortunately, it seems to be an intrinsic property of high molecular weight chain molecules to aggregate under conditions of crystallization in form of highly complex morphological structures in which parts of the chains remain amorphous and form a matrix in which microscopic domains of crystalline chain segments of the same molecules are embedded. For some time it was even believed that perfect polymer single crystals do not exist at all, mainly because the phenomenon of chain folding observed in polymer crystallization is so general and structure-independent that the formation of extended chain crystals of polymers seemed to be impossible (1). The extensive research undertaken in the area of polymer crystallization leaves indead little hope for successful attempts to prepare a polymer backbone first by one or the other methods of polymer chemistry e. g. polymer charge-transfer-complexes of the type TTF-TCNQ or polyconjugated molecules or even more complex molecules like the ones proposed by Little (2) with the aim to crystallize these products afterwards into single-crystal-like or at least polycrystalline materials.


Polymer Backbone Thermal Polymerization Optically Detect Magnetic Resonance Chain Direction Autocatalytic Effect 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    For an extensive discussion of the problems encountered in polymer crystallization and morphology it is refered to B. Wunderlich “Macromolecular Physics, Academic Press, New York 1976Google Scholar
  2. 2.
    W. A. Little, J. Polymer Sci. C 17, 3 (1967)Google Scholar
  3. 3.
    G. Wegner, Z. Naturforschg. 24b, 824 (1969)Google Scholar
  4. 4. a)
    F. L. Hirshfeld and G. M. J. Schmidt, J. Polymer Sci. A2, 2181 (1964),Google Scholar
  5. 4. b)
    G. M. J. Schmidt in Reactivity of the Photoexcited Molecule, p. 227 f. Interscience (1967)Google Scholar
  6. 5.
    There are several reviews discussing the implications of organic solid-state chemistry both to preparative and structural chemistry, among others:Google Scholar
  7. 5. a)
    M. D. Cohen and B. S. Green, Chemistry in Britain, 9, 490 (1973)Google Scholar
  8. 5. b)
    J. M. Thomas, Phil. Trans. Roy. Soc. (London) A277, 251 (1974)Google Scholar
  9. 5. c)
    G. Wegner, Pure & Appl. Chem. 49, 443 (1977)Google Scholar
  10. 5. d)
    G. Wegner, A. Munoz-Escalona and E. W. Fischer, Makromol. Chem. Suppl. 1, 521 (1975)Google Scholar
  11. 6.
    J. Kaiser, G. Wegner, and E. W. Fischer, Israel J. Chem. 10, 157 (1972)Google Scholar
  12. 7.
    R. H. Baughman, J. Polym. Sci., Polym. Phys. Ed. 12, 1511 (1974)Google Scholar
  13. 8.
    D. Bloor et al., J. Mater. Sci. 10, 1678, 1689 (1975)CrossRefGoogle Scholar
  14. 9.
    The only other case besides the diacetylenes where formation of a solid solution of the growing polymer product with the parent monomer matrix has been reported refers to the polymerization of SN to (SN) (R. H. Baughman and R. R.Chance, J. Polym. Sci. Polym. Phys. Ed.x 14, 2019 (1976)Google Scholar
  15. 10.
    R. H. Baughman, The Solid-state Synthesis and Properties of Photoconducting, Metallic and Superconducting Polymer Crystals in “Contemporary Topics in Polymer Science, Vol. 2, E. M. Pearce and I. R. Schaefgen, Eds. Plenum Press 1977, p. 205CrossRefGoogle Scholar
  16. 11.
    K. Takeda and G. Wegner, Makromol. Chem. 160, 349 (1972)CrossRefGoogle Scholar
  17. 12.
    G. C. Stevens and D. Bloor, Chem. Phys. Letters 40, 37 (1976)CrossRefGoogle Scholar
  18. 13.
    H. Eichele, M. Schwoerer, R. Huber and D. Bloor, Chem. Phys. Letters, 42, 342 (1976)CrossRefGoogle Scholar
  19. 14.
    G. Wegner, Organic Linear Polymers with Conjugated Double Bonds in Chemistry and Physics of One-Dimensional Metals, H. J. Keller, Ed., Plenum Press 1977, p. 297Google Scholar
  20. 15.
    E. Hädicke et al., Angew. Chem. 83. 253 (1971)CrossRefGoogle Scholar
  21. 16.
    D. Kobelt and H. Paulus, Acta Cryst. B30, 232 (1974)Google Scholar
  22. 17.
    J. B. Lando, D. Day and V. Enkelmann, ACS-Polymer Preprints 18, 1, 190 (1977)Google Scholar
  23. 17a.
    D. Day and J. B. Lando, J. Polymer Sci., Polym. Phys. Ed. 16, 1009 (1978)CrossRefGoogle Scholar
  24. 18.
    V. En kelmann and J. B. Lando, Acta Cryst. (1978) in pressGoogle Scholar
  25. 19.
    A. J. Melveger and R. H. Baughman, J. Polymer Sci., Polym. Phys. Ed. 11, 603 (1973)Google Scholar
  26. 20.
    R. H. Baughman, J. D. Witt and K. C. Yee, J. Chem. Phys. 60, 4755 (1974)CrossRefGoogle Scholar
  27. 21.
    D. Bloor, D. J. Ando, F.H. Preston and G. C. Stevens, Chem. Phys. Letters 24, 407 (1974)CrossRefGoogle Scholar
  28. 22.
    D. Bloor, F. H. Preston, D. J. Ando and D. N. Batchelder “Resonant Raman Scattering from Diacetylene Polymers” in: Structural Studies of Macromolecules by Spectroscopic Methods p. 91 f., K. J. Ivin, Ed. Wiley 1975Google Scholar
  29. 23.
    W. Schermann and G. Wegner, Makromol. Chem. 175, 667 (1974)CrossRefGoogle Scholar
  30. 24.
    E. G. Wilson, J. Phys. C: Solid-State Phys. 8, 727 (1975)CrossRefGoogle Scholar
  31. 25.
    G. Wegner, Makromol. Chem. 145, 85 (1971)CrossRefGoogle Scholar
  32. 26.
    G. Wegner, Makromol. Chem. 154, 35 (1972)CrossRefGoogle Scholar
  33. 27.
    J. M. Schultz, J. Mater. Sci. 12, 2258 (1976)CrossRefGoogle Scholar
  34. 28.
    W. Schermann, J.O. Williams, J. M. Thomas and G. Wegner, J. Polymer Sci., Polymer Phys. Ed. 13, 753 (1975)CrossRefGoogle Scholar
  35. 29.
    G. Wegner and W. Schermann, Colloid & Polymer Sci., 252, 655 (1974)CrossRefGoogle Scholar
  36. 30. a)
    V. Enkelmann and G. Wegner, Makromol. Chem. 178, 635 (1977)CrossRefGoogle Scholar
  37. 30. b)
    V. Enkelmann, Acta Cryst. B33, 2842 (1977)Google Scholar
  38. 31.
    V. Enkelmann and G. Wegner, Angew. Chem. 89, 432 (1977)CrossRefGoogle Scholar
  39. 32.
    V. Enkelmann, R. J. Leyrer and G. Wegner, J. Amer. Chem. Soc, in pressGoogle Scholar
  40. 33.
    D. Bloor, F. H. Preston and D. J. Ando, Chem. Phys. Letters, 38, 33 (1976)CrossRefGoogle Scholar
  41. 34.
    B. Reimer, H. Baessler, J. Hesse and G. Weiser, phys. stat. sol. (b) 73, 709 (1976)CrossRefGoogle Scholar
  42. 35.
    C. J. Eckhardt, H. Müller, J. Tylicki and R. R. Chance, J. Chem. Phys. 65, 4311 (1976)CrossRefGoogle Scholar
  43. 36.
    M. Schott, F. Batallan and M. Bertault, Chem. Phys. Lett. 53, 443 (1978)CrossRefGoogle Scholar
  44. 37. a)
    C. Flytzanis, C. Cojan and G. P. Agrawal, Nuovo Cimento 39b, 488 (1977)Google Scholar
  45. 37. b)
    G. P. Agrawal, C. Cojan and C. Flytzanis, Phys. Rev. Letters, 38, 711 (1977)CrossRefGoogle Scholar
  46. 38.
    D. Bloor and F. H. Preston, phys. stat. sol. (a) 37, 427 (1976)CrossRefGoogle Scholar
  47. 39.
    D. Bloor and F. H. Preston, phys. stat. sol. 39, 607 (1977)CrossRefGoogle Scholar
  48. 40.
    D. Bloor, D. N. Batchelder and F. H. Preston, phys. stat. sol. 40, 279 (1977)CrossRefGoogle Scholar
  49. 41.
    H. A. Pohl and R. P. Chartoff, J. Polymer Sci. A2, 2787 (1964)Google Scholar
  50. 42.
    N. R. Byrel, F. K. Kleist and D. N. Stamires, J. Polymer Sci., Phys. Ed. 10, 957 (1972)Google Scholar
  51. 43.
    L. S. Singer and J. Kommandeur, J. Chem. Phys. 34, 133 (1961)CrossRefGoogle Scholar
  52. 44.
    A. A. Berlin, Vysokomol. Soed. A13, 2429 (1971)Google Scholar
  53. 45.
    J.A. Pople and S. H. Walmsley, Mol.Phys. 5, 15 (1962)CrossRefGoogle Scholar
  54. 46.
    G. F. Kventsel and Yu. A. Kruglyak, Theor. Chem. Acta 12, 1 (1968)CrossRefGoogle Scholar
  55. 47.
    G. C. Stevens and D. Bloor, J. Polymer Sci., Polym. Phys. Ed. 13, 2411 (1975)CrossRefGoogle Scholar
  56. 48.
    G. C. Stevens and D. Bloor, phys. stat. sol. (a) 45, 483 (1978)CrossRefGoogle Scholar
  57. 48a.
    G. C. Stevens and D. Bloor, phys. stat. sol. 46, 141 (1978)CrossRefGoogle Scholar
  58. 48b.
    G. C. Stevens and D. Bloor, phys. stat. sol. 46, 619 (1978)CrossRefGoogle Scholar
  59. 49.
    Some implications of such a defect and further defects derived from it by consecutive bond rotations (“orbital-flip-defect”) on the spectral properties of polydiacetylenes have been discussed (50)Google Scholar
  60. 50.
    R. H. Baughman and R. R. Chance, J. Appl. Phys. 47, 4295 (1976)CrossRefGoogle Scholar
  61. 51.
    R.J. Leyrer, G. Wegner and W. Wettling, Ber. Bunsenges. Phys. Chem. 82, 697 (1978)Google Scholar
  62. 52.
    D. N. Batchelder and D. Bloor “Strain Dependence of the Vibrational Modes of a Diacetylene Crystal”, PreprintGoogle Scholar
  63. 53.
    R. H. Baughman, H. Gleiter and N. Sendfeld, J. Polymer Sci., Polym. Phys. Ed. 13 . 1871 (1975)CrossRefGoogle Scholar
  64. 54.
    F. C. Frank, Proc. R. Soc. London, Ser. A 319, 127 (1970)CrossRefGoogle Scholar
  65. 55.
    Y. Kobayashi and A. Keller, Polymer 11, 114 (1970)CrossRefGoogle Scholar
  66. 56.
    R. H. Baughman and E. A. Turi, J. Polymer Sci., Polym. Phys. Ed. 11, 2453 (1973)Google Scholar
  67. 57.
    D. N. Batchelder, J. Polymer Sci., Polymer Phys. Ed. 14, 1235 (1976)CrossRefGoogle Scholar
  68. 58.
    R.W. Munn, J. Phys. C. 5, 535 (1972)CrossRefGoogle Scholar
  69. 59.
    R. J. Young, D. Bloor, D. N. Batchelder and C. L. Hubble J. Mater. Sci. 13, 62 (1978) and references therinCrossRefGoogle Scholar
  70. 60.
    K. C. Yee and R. R. Chance, J. Polym. Sci., Polym. Phys. Ed. 16, 431 (1978)CrossRefGoogle Scholar
  71. 61.
    V. Enkelmann, G. Schleyer, G. Wegner, H. Eichele and M. Schwoerer Chem. Phys. Letters 52, 314 (1977)CrossRefGoogle Scholar
  72. 62.
    The monomer undergoes a photochemical isomerization if solutions are exposed even to day light for some time. Crystallization should be carried out in the dark.Google Scholar
  73. 63.
    A. Warshel and E. Huler, Chem. Phys. 6, 463 (1974)CrossRefGoogle Scholar
  74. 64.
    H. Eichele, M. Schworer and J. K. von Schütz, Chem. Phys. Letters, 56, 208 (1978)CrossRefGoogle Scholar
  75. 65.
    P. A. Apgar and K. C. Yee, Acta Cryst. B34, 957 (1978)Google Scholar
  76. 66.
    R. J. Hood, H. Müller, C. J. Eckhardt, R. R. Chance and K.C. Yee, Chem. Phys. Letters 54, 295 (1978)CrossRefGoogle Scholar
  77. 67.
    J. J. Mayerle and M. A. Flandera, Acta Crst. B34, 1374, (1978)CrossRefGoogle Scholar
  78. 68.
    D. Bloor, W. Hersel and D. N. Batchelder, Chem. Phys. Letters 45, 411 (1977)CrossRefGoogle Scholar
  79. 69.
    Z. Igbal, R. R. Chance and R. H. Baughman, J. Chem. Phys. 66, 5520 (1977)CrossRefGoogle Scholar
  80. 70.
    G. Wegner, G. Arndt, H. J. Graf and M. Steinbach in “Reactivity of Solids” J. Wood et al. Eds., Plenum Press 1977, p. 487 f.Google Scholar
  81. 71.
    G. J. Exharos, W. M. Risen and R. H. Baughman, J. Amer. Chem. Soc. 98, 481 (1976)CrossRefGoogle Scholar
  82. 72.
    R. R. Chance, R. H. Baughman, A. F. Preziosi and E. A. Turi, Bull. Amer. Phys. Soc. 22, 408 (1977)Google Scholar
  83. 73.
    R. R. Chance, R. H. Baughman, H. Müller and C. J. Eckhardt, J. Chem. Phys. 67, 3616 (1977)CrossRefGoogle Scholar
  84. 74.
    R. H. Baughman and R. R.Chance “Fully conjugated polymer crystals: Solid-state synthesis and properties of the polydiacetylenes” Ann. New York Acad. Sci., in pressGoogle Scholar
  85. 75.
    B. Tieke, Thesis, University of Freiburg, 1978Google Scholar
  86. 76.
    V. Enkelmann and G. Schleier, unpublishedGoogle Scholar
  87. 77.
    H. Eichele, Thesis, University of Bayreuth, 1978, p. 124 f.Google Scholar
  88. 78.
    J. J. Mayerle and T. C. Clarke, Acta Cryst. B34, 143 (1978)Google Scholar
  89. 79.
    V. Enkelmann, private communicationGoogle Scholar
  90. 80.
    C. Kröhnke, private communicationGoogle Scholar
  91. 81.
    B. Tieke, G. Wegner, D. Naegele and H. Ringsdorf, Angew. Chem. Int. Ed. 15, 764 (1976)CrossRefGoogle Scholar
  92. 82.
    B. Tieke, H.-J. Graf, G. Wegner et al., Colloid & Polymer Sci., 255, 521 (1977)CrossRefGoogle Scholar
  93. 83.
    B. Tieke and G. Wegner, in “Topics in Surface Chemistry”, Plenum Press 1978 p. 121CrossRefGoogle Scholar
  94. 84.
    B. Tieke, G. Lieser and G. Wegner, J. Polym. Sci., Polym. Chem. Ed.. in pressGoogle Scholar
  95. 85.
    D. Day and H. Ringsdorf, J. Polym. Sci. Polym. Letters Ed. 16, 205 (1978)CrossRefGoogle Scholar
  96. 86.
    K. B. Blodgett, J. Amer. Chem. Soc. 57, 1007 (1935); for a complete description of the technique and its application see ref. (87)CrossRefGoogle Scholar
  97. 87.
    H. Kuhn and D. Möbius, Angew. Chem. Int. Ed. 10, 620 (1971)CrossRefGoogle Scholar
  98. 88.
    B. Tieke and G. Wegner, Makromol. Chem. 179, 1639 (1978)CrossRefGoogle Scholar
  99. 89.
    K. Lochner, B. Reimer and H. Bässler, Chem. Phys. Letters 41, 388 (1976)CrossRefGoogle Scholar
  100. 90.
    J. Knecht, B. Reimer and H. Bässler, Chem. Phys. Letters 49, 327 (1977)CrossRefGoogle Scholar
  101. 91.
    G.C. Stevens, D. Bloor and P. M. Williams, Chem. Phys. 28, 399 (1978)CrossRefGoogle Scholar
  102. 92.
    J. Knecht and H. Bässler, Chem. Phys. in pressGoogle Scholar
  103. 93.
    B. Reimer and H. Bässler, phys. stat. sol. (a) 32, 435 (1975)CrossRefGoogle Scholar
  104. 94.
    R. R. Ehance and R. H. Baughman, J. Chem. Phys. 64, 3889 (1976)CrossRefGoogle Scholar
  105. 95.
    K. Lochner, B. Reimer and H. Bässler, phys. stat. sol. (b) 76, 533 (1976)CrossRefGoogle Scholar
  106. 96.
    R. Jankowiak, J. Kalinowski, B. Reimer and H. Bässler, Chem. Phys. Letters 54, 483 (1978)CrossRefGoogle Scholar
  107. 97.
    M. R. Philpott, Chem. Phys. Letters 50, 18 (1977)CrossRefGoogle Scholar
  108. 98.
    D. S. Boudreaux and R. R. Chance, Chem. Phys. Letters 51, 273 (1977)CrossRefGoogle Scholar
  109. 99.
    M. Kertesz, J. Koller and A. Azman, Chem. Phys. 27, 273 (1978)CrossRefGoogle Scholar
  110. 100.
    H. Müller, C. J. Eckhardt, R. R. Chance and R. Baughman, Chem. Phys. Letters 50, 22 (1977)CrossRefGoogle Scholar
  111. 101.
    K. Lochner, H. Bässler, B. Tieke and G. Wegner, phys. stat. sol. (b) 1978 in pressGoogle Scholar
  112. 102.
    V. Enkelmann, personal communicationGoogle Scholar
  113. 103.
    C. C. Sauteret et al. Phys. Rev. Letters 36, 956 (1976)CrossRefGoogle Scholar
  114. 104.
    J. P. Hermann and J. Ducuing, J. Appl. Phys. 45, 5100 (1974)CrossRefGoogle Scholar
  115. 105.
    C. Cojan, G. Agrawal and C. Flytzanis, Phys. Rev. B2, 909 (1977)Google Scholar
  116. 106.
    G. P. Agrawal, C. Cojan and C. Flytzanis, PreprintGoogle Scholar
  117. 107.
    R. Huber, M. Schworer, C. Bubeck and H. Sixl, Preprint “The Sign of D in the Triple Carbene of a Polydiacetylene Single Crystal) (PTS)Google Scholar
  118. 108.
    H. Sixl, W. Hersel and H. C. Wolf, Chem. Phys. Letters 53, 39 (1978)CrossRefGoogle Scholar
  119. 109.
    C. Bubeck, H. C. Wolf and H. Sixl, Preprint “Photopolymerization of Diacetylene Single-Crystals II. ESR-SpectroscopyGoogle Scholar
  120. 110.
    H. Eichele and M. Schwoerer, phys. stat. sol. (a) in pressGoogle Scholar
  121. 111.
    R.R. Chance, G. N. Patel, E. A. Turi and Y. P. Khanna, J. Amer. Chem. Soc. 100, 1307 (1978)CrossRefGoogle Scholar
  122. 112.
    A.R.McGhie, P.S. Kalyanaraman and A. F. Garito, J. Polymer Sci., Polym. Phys. Ed. in pressGoogle Scholar
  123. 113.
    R. R. Chance and J. M. Sowa, J. Amer. Chem. Soc. 99, 6703 (1977)CrossRefGoogle Scholar
  124. 114.
    R. R. Chance and G. N. Patel, J. Polym. Sci., Polym. Phys. Ed. 16, 859 (1978)CrossRefGoogle Scholar
  125. 115.
    R.H. Bauhgman, J. Chem. Phys. 68, 3110 (1978)CrossRefGoogle Scholar
  126. 116.
    R. H. Baughman and K. C. Yee, J. Polymer Sci., Pol. Chem. Ed. 12, 2467 (1974)CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1979

Authors and Affiliations

  • G. Wegner
    • 1
  1. 1.Institut für Makromolekulare ChemieUniversität — Hermann-Staudinger-HausFreiburgWest Germany

Personalised recommendations