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Doped Polyacetylene

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Acetylene and Its Polymers

Part of the book series: SpringerBriefs in Molecular Science ((BRIESFHISTCHEM))

Abstract

This chapter will review the historical development of doped forms of polyacetylene that resulted in materials with increased conductivity. These highly conductive forms of polyacetylene were achieved via oxidation or reduction of the neutral polymer and such redox modified conjugated polymers are often referred to as doped materials in analogy to the doping of inorganic semiconductors such as silicon. The discussion will begin with the initial efforts of Donald Berets and Dorian Smith in 1968 and will continue up through the work of Herbert Naarmann in the 1980s.

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Notes

  1. 1.

    See Chap. 5.

  2. 2.

    See Chap. 5.

  3. 3.

    This was quickly exceeded by the conductivity of the stretch-oriented, AsF5-doped films reported in April of that same year [68].

References

  1. Watson WH Jr, McMordie WC Jr, Lands LG (1961) Polymerization of alkynes by Ziegler-type catalyst. J Polym Sci 55:137–144

    Article  CAS  Google Scholar 

  2. Hatano M, Kanbara S, Okamoto S (1961) Paramagnetic and electric properties of polyacetylene. J Polym Sci 51:S26–S29

    Article  CAS  Google Scholar 

  3. Shirakawa H, Ito T, Ikeda S (1978) Electrical properties of polyacetylene with various cis-trans compositions. Makromol Chem 179:1565–1573

    Article  CAS  Google Scholar 

  4. Rasmussen SC (2017) Early history of conductive organic polymers. In: Zhang Z, Rouabhia M, Moulton SE (eds) Conductive polymers: electrical interactions in cell biology and medicine. CRC Press, Boca Raton, Chapter 1

    Google Scholar 

  5. McNeill R, Siudak R, Wardlaw JH, Weiss DE (1963) Electronic conduction in polymers. Aust J Chem 16:1056–1075

    Article  CAS  Google Scholar 

  6. Bolto BA, Weiss DE (1963) Electronic conduction in polymers. II. The electrochemical reduction of polypyrrole at controlled potential. Aust J Chem 16:1076–1089

    Article  CAS  Google Scholar 

  7. Bolto BA, McNeill R, Weiss DE (1963) Electronic conduction in polymers. III. Electronic Properties of polypyrrole. Aust J Chem 16:1090–1103

    Article  CAS  Google Scholar 

  8. Jozefowicz M, Yu LT (1966) Relations entre propriétés chimiques et électrochimiques de semi-conducteurs macromoléculaires. Rev Gen Electr 75:1008–1013

    CAS  Google Scholar 

  9. Yu LT, Jozefowicz M (1966) Conductivité et constitution chimique pe semi-conducteurs macromoléculaires. Rev Gen Electr 75:1014–1018

    CAS  Google Scholar 

  10. De Surville R, Jozefowicz M, Yu LT, Perichon J, Buvet R (1968) Electrochemical chains using protolytic organic semiconductors. Electrochim Acta 13:1451–1458

    Article  Google Scholar 

  11. Jozefowicz M, Yu LT, Perichon J, Buvet R (1969) Proprietes nouvelles des polymeres semiconducteurs. J Polym Sci Part C Polym Symp 22:1187–1195

    Article  Google Scholar 

  12. Berets DJ, Smith DS (1968) Electrical properties of linear polyacetylene. Trans Faraday Soc 64:823–828

    Article  CAS  Google Scholar 

  13. Morrissey S (2002) Obituaries. Chem Eng News 80(20):56

    Article  Google Scholar 

  14. Anon (2002) Donald Joseph Berets. Harvard Magazine, May–June

    Google Scholar 

  15. Berets DJ (1949) Studies on the detonation of explosive gas mixtures. Ph.D. Dissertation, Harvard University

    Google Scholar 

  16. Anon (2010) Dorian Sevcik Smith Obituary. Wilmington Star-News, December 15

    Google Scholar 

  17. Smith DS (1958) Observations on the rare-earths: chemical and electrochemical studies in non-aqueous solvents. Ph.D. Dissertation. University of Illinois

    Google Scholar 

  18. Illinois State Athletics Percy Hall of Fame (1990) 1950 Football. http://goredbirds.com/hof.aspx?hof=281. Accessed 1 Apr 2018

  19. State of Illinois (1954) Proceedings of the Teachers College Board of the State of Illinois, July 1, 1953–June 30, 1954, pp 155–156

    Google Scholar 

  20. Shirakawa H, Ito T, Ikeda S (1973) Raman scattering and electronic spectra of poly(acetylene). Polym J 4:460–462

    Article  CAS  Google Scholar 

  21. Ito T, Shirakawa H, Ikeda S (1974) Simultaneous polymerization and formation of poly-acetylene film on the surface of concentrated soluble Ziegler-type catalyst solution. J Polym Sci Polym Chem Ed 12:11–20

    Article  CAS  Google Scholar 

  22. Shirakawa H, Louis EJ, MacDiarmid AG, Chiang CK, Heeger AJ (1977) Synthesis of electrically conducting organic polymers: Halogen derivatives of polyacetylene, (CH)x. J Chem Soc Chem Commun 578–580

    Google Scholar 

  23. Chiang CK, Fincher CR Jr, Park YW, Heeger AJ, Shirakawa H, Louis BJ, Gau SC, MacDiarmid AG (1977) Electrical conductivity in doped polyacetylene. Phys Rev Lett 39:1098–1101

    Article  CAS  Google Scholar 

  24. MacDiarmid AG, Mikulski CM, Russo PJ, Saran MS, Garito AF, Heeger AJ (1975) Synthesis and structure of the polymeric metal, (SN)x, and its precursor, S2N2. J Chem Soc Chem Commun 476–477

    Google Scholar 

  25. Mikulski CM, Russo PJ, Saran MS, MacDiarmid AG, Garito AF, Heeger AJ (1975) Synthesis and structure of metallic polymeric sulfur nitride, (SN)x, and its precursor, disulfur dinitride, S2N2. J Am Chem Soc 97:6358–6363

    Google Scholar 

  26. Chiang CK, Cohen MJ, Garito AF, Heeger AJ, Mikulski CM, MacDiarmid AG (1976) Electrical conductivity of (SN)x. Solid State Commun 18:1451–1455

    Article  CAS  Google Scholar 

  27. Chiang CK, Cohen MJ, Peebles DL, Heeger AJ, Akhtar M, Kleppinger J, MacDiarmid AG, Milliken J, Moran MJ (1977) Transport and optical properties of polythiazyl bromides: (SNBr 0.4)x. Solid State Commun 23:607–612

    Article  CAS  Google Scholar 

  28. MacDiarmid AG (2001) Alan G. MacDiarmid. In: Frängsmyr T (ed) Les Prix Nobel. The Nobel prizes 2000. Nobel Foundation, Stockholm, pp 183–190

    Google Scholar 

  29. MacDiarmid AG (2005) Oral history interview by Cyrus Mody at University of Pennsylvania, Philadelphia, Pennsylvania. Oral History Transcript #0325. Chemical Heritage Foundation, Philadelphia

    Google Scholar 

  30. Hall N (2003) Twenty-five years of conducting polymers. Chem Commun 1–4

    Google Scholar 

  31. Hargittai B, Hargittai I (2005) Alan G. MacDiarmid. In: candid science V: conversations with famous scientists. Imperial College Press, London, pp 401–409

    Google Scholar 

  32. MacDiarmid AG (1949) Preparation of mono-halogen substituted compounds of sulphur nitride. Nature 164:1131–1132

    Article  CAS  Google Scholar 

  33. MacDiarmid AG (2001) “Synthetic metals”: a novel role for organic polymers (Nobel lecture). Angew Chem Int Ed 40:2581–2590

    Article  CAS  Google Scholar 

  34. Halford B (2007) Alan MacDiarmid Dies at 79. Chem Eng News 85(7):16

    Article  Google Scholar 

  35. MacDiarmid AG (1953) Isotopic Exchange in complex cyanide—simple cyanide systems. Ph.D. Dissertation. University of Wisconsin-Madison

    Google Scholar 

  36. MacDiarmid AG (1955) The chemistry of some new derivatives of the silyl radical. Ph.D. Dissertation. University of Cambridge

    Google Scholar 

  37. Heeger AJ (2001) Alan J. Heeger. In: Frängsmyr T (ed) Les Prix Nobel. The Nobel prizes 2000. Nobel Foundation, Stockholm, pp 139–143

    Google Scholar 

  38. Heeger AJ (2001) Semiconducting and metallic polymers: the fourth generation of polymeric materials (Nobel lecture). Angew Chem Int Ed 40:2591–2611

    Article  CAS  Google Scholar 

  39. Heeger AJ (2016) Never lose your nerve! World Scientific Publishing, Singapore, pp 23–26

    Google Scholar 

  40. Heeger AJ (2016) Never lose your nerve! World Scientific Publishing, Singapore, pp 34–39

    Google Scholar 

  41. Heeger AJ (2016) Never lose your nerve!. World Scientific Publishing, Singapore, p 55

    Google Scholar 

  42. Heeger AJ (2016) Never lose your nerve! World Scientific Publishing, Singapore, pp 68–71

    Google Scholar 

  43. Heeger AJ (2016) Never lose your nerve! World Scientific Publishing, Singapore, pp 77–91

    Google Scholar 

  44. Heeger AJ (1961) Studies on the magnetic properties of canted antiferromagnets. Ph.D. Dissertation. University of California, Berkeley

    Google Scholar 

  45. Heeger AJ (2016) Never lose your nerve! World Scientific Publishing, Singapore, pp 181–191

    Google Scholar 

  46. Heeger AJ (2016) Never lose your nerve! World Scientific Publishing, Singapore, pp 132–150

    Google Scholar 

  47. Walatka VV, Labes MM, Perlstein JH (1973) Polysulfur nitride—a one-dimensional chain with a metallic ground state. Phys Rev Lett 31:1139–1142

    Article  CAS  Google Scholar 

  48. Hsu C, Labes MM (1974) Electrical conductivity of polysulfur nitride. J Chem Phys 61:4640–4645

    Article  CAS  Google Scholar 

  49. Labes MM, Love P, Nichols LF (1979) Polysulfur nitride-a metallic, superconducting polymer. Chem Rev 79:1–15

    Article  CAS  Google Scholar 

  50. Mikulski CM, Russo PJ, Saran MS, MacDiarmid AG, Garito AF, Heeger AJ (1975) Synthesis and structure of metallic polymeric sulfur nitride, (SN)x, and its precursor, disulfur dinitride, S2N2. J Am Chem Soc 97:6358–6363

    Article  CAS  Google Scholar 

  51. Mikulski CM, MacDiarmid AG, Garito AF, Heeger AJ (1976) Stability of polymeric sulfur nitride, (SN)x, to air, oxygen, and water vapor. Inorg Chem 15:2943–2945

    Article  CAS  Google Scholar 

  52. Cohen MJ, Garito AF, Heeger AJ, MacDiarmid AG, Mikulski CM, Saran MS, Kleppinger J (1976) Solid state polymerization of S2N2 to (SN)x. J Am Chem Soc 98:3844–3948

    Article  CAS  Google Scholar 

  53. Rasmussen SC (2016) On the origin of ‘synthetic metals’. Mater Today 19:244–245

    Article  Google Scholar 

  54. Rasmussen SC (2016) On the origin of “synthetic metals”: Herbert McCoy, Alfred Ubbelohde, and the development of metals from nonmetallic elements. Bull Hist Chem 41:64–73

    CAS  Google Scholar 

  55. Kaner RB, MacDiarmid AG (1988) Plastics that conduct electricity. Sci Am 258(2):106–111

    Article  CAS  Google Scholar 

  56. Hargittai I (2011) Drive and curiosity: what fuels the passion for science. Prometheus Books, Amherst, pp 173–190

    Google Scholar 

  57. Shirakawa H (2001) Hideki Shirakawa. In: Frängsmyr T (ed) Les Prix Nobel. The Nobel prizes 2000. Nobel Foundation, Stockholm, pp 213–216

    Google Scholar 

  58. Shirakawa H (2001) The discovery of polyacetylene film: the dawning of an era of con-ducting polymers (Nobel lecture). Angew Chem Int Ed 40:2574–2580

    Article  Google Scholar 

  59. Ito T, Shirakawa H, Ikeda S (1975) Thermal cis-trans isomerization and decomposition of polyacetylene. J Polym Sci Polym Chem Ed 13:1943–1950

    Article  CAS  Google Scholar 

  60. Shirakawa H (2001) The discovery of polyacetylene film: the dawning of an era of con-ducting polymers. In: Frängsmyr T (ed) Les Prix Nobel. The Nobel prizes 2000. Nobel Foundation, Stockholm, pp 217–226

    Google Scholar 

  61. Shirakawa H (2001) Nobel lecture: the discovery of polyacetylene film—the dawning of an era of conducting polymers. Rev Modern Phys 73:713–718

    Article  CAS  Google Scholar 

  62. Shirakawa H (2002) The discovery of polyacetylene film. The dawning of an era of con-ducting polymers. Synth Met 125:3–10

    Article  CAS  Google Scholar 

  63. Chiang CK, Gau SC, Fincher CR Jr, Park YW, MacDiarmid AG, Heeger AJ (1978) Polyacetylene, (CH)x: n-type and p-type doping and compensation. App Phys Lett 33:18–20

    Article  CAS  Google Scholar 

  64. Chiang CK, Park YW, Heeger AJ, Shirakawa H, Louis EJ, MacDiarmid AG (1978) Conducting polymers: Halogen doped polyacetylene. J Chem Phys 69:5098–5104

    Article  CAS  Google Scholar 

  65. Maricq MM, Waugh JS, MacDiarmid AG, Shirakawa H, Heeger AJ (1978) Carbon-13 nuclear magnetic resonance of cis- and trans-polyacetylenes. J Am Chem Soc 100:7729–7730

    Article  CAS  Google Scholar 

  66. Chiang CK, Druy MA, Gau SC, Heeger AJ, Louis EJ, MacDiarmid AG, Park YW, Shirakawa H (1978) Synthesis of highly conducting films of derivatives of polyacetylene, (CH)x. J Am Chem Soc 100:1013–1015

    Article  CAS  Google Scholar 

  67. Fincher CR Jr, Peebles DL, Heeger AJ, Druy MA, Matsumura Y, MacDiarmid AG, Shirakawa H, Ikeda S (1978) Anisotropic optical properties of pure and doped polyacetylene. Solid State Commun 27:489–494

    Article  CAS  Google Scholar 

  68. Park YW, Druy MA, Chiang CK, MacDiarmid AG, Heeger AJ, Shirakawa H, Ikeda S (1979) Anisotropic electrical conductivity of partially oriented polyacetylene. J Polym Sci Polym Lett Ed 17:195–201

    Article  CAS  Google Scholar 

  69. Duke CB, Paton A, Salaneck WR, Thomas HR, Plummer EW, Heeger AJ, MacDiarmid AG (1978) Electronic structure of polyenes and polyacetylene. Chem Phys Lett 59:146–150

    Article  CAS  Google Scholar 

  70. Goldberg IB, Crowe HR, Newman PR, Heeger AJ, MacDiarmid AG (1979) Electron spin resonance of polyacetylene and AsF5-doped polyacetylene. J Chem Phys 70:1132–1136

    Article  CAS  Google Scholar 

  71. Nigrey PJ, MacDiarmid AG, Heeger AJ (1979) Electrochemistry of polyacetylene, (CH)x: electrochemical doping of (CH)x films to the metallic state. J Chem Soc Chem Commun 594–595

    Google Scholar 

  72. Chiang CK, Heeger AJ, Macdiarmid AG (1979) Synthesis, structure, and electrical properties of doped polyacetylene. Ber Bunsen-Ges 78983:407–417

    Article  Google Scholar 

  73. Salaneck WR, Thomas HR, Duke CB, Paton A, Plummer EW, Heeger AJ, MacDiarmid AG (1979) J Chem Phys 71:2044–2050

    Google Scholar 

  74. Wnek GE, Chien JCW, Karasz FE, Druy MA, Park YW, MacDiarmid AG, Heeger AJ (1979) Variable-density conducting polymers: conductivity and thermopower studies of a new form of polyacetylene: (CH)x. J Polym Sci Polym Lett Ed 17:779–786

    Article  CAS  Google Scholar 

  75. Weinberger BR, Kaufer J, Heeger AJ, Pron A, MacDiarmid AG (1979) Magnetic susceptibility of doped polyacetylene. Phys Rev B 20:223–230

    Article  CAS  Google Scholar 

  76. Fincher CE Jr, Ozaki M, Tanaka M, Peebles D, Lauchlan L, Heeger AJ (1979) Electronic structure of polyacetylene: optical and infrared studies of undoped semiconducting (CH)x and heavily doped metallic (CH)x. Phys Rev B 20:1589–1601

    Article  CAS  Google Scholar 

  77. Karasz FE, Chien JCW, Galkiewicz R, Wnek GE, Heeger AJ, MacDiarmid AG (1979) Nascent morphology of polyacetylene. Nature 282:286–288

    Article  CAS  Google Scholar 

  78. Theophilou N, Aznar R, Munardi A, Sledz J, Schue F, Naarnann H (1986) E.S.R. Study of the Ti(OBu)4 catalyst mixture in silicone oil with regard to the synthesis of homogeneous and highly conducting (CH)x. Synth Metals 16:337–342

    Article  CAS  Google Scholar 

  79. Naarmann H (1990) The development of electrically conducting polymers. Adv Mater 2:345–348

    Article  CAS  Google Scholar 

  80. Naarmann H (1959) On the identification of constituents of the poison of some bird spiders. Ph.D. Dissertation. Julius-Maximilians-Universität Würzburg

    Google Scholar 

  81. Munardi A, Aznar R, Theophilou N, Sledz J, Schue F, Naarnann H (1987) Morphology of polyacetylene produced in the presence of the soluble catalyst Ti(OnBu)4-n-BuLi. Eur Polym J 23:11–14

    Article  CAS  Google Scholar 

  82. Munardi A, Theophilou N, Aznar R, Sledz J, Schue F, Naarnann H (1987) Polymerization of acetylene with Ti(OC4H9)4/butyllithium as catalyst system and silicone oil as reaction medium. Makromol Chem 188:395–399

    Article  CAS  Google Scholar 

  83. Theophilou N, Aznar R, Munardi A, Sledz J, Schue F, Naarnann H (1987) Polymerization of acetylene with new catalytic systems and optimization of the properties of the polymers. J Macromol Sci Chem A24:797–812

    Article  CAS  Google Scholar 

  84. Naarmann H, Theophilou N (1987) New process for the production of metal-like, stable polyacetylene. Synth Metals 22:1–8

    Article  CAS  Google Scholar 

  85. Basescu N, Liu ZX, Moses D, Heeger AJ, Naarmann H, Theophilou N (1987) High electrical conductivity in doped polyacetylene. Nature 327:403–405

    Article  CAS  Google Scholar 

  86. Schimmel T, Rieβ W, Gmeiner J, Denninger G, Schwoerer M, Naarmann H, Theophilou N (1988) DC-Conductivity on a new type of highly conducting polyacetylene, N-(CH)x. Solid State Commun 65:1311–1315

    Article  CAS  Google Scholar 

  87. Naarmann H, Theophilou N (1989) Influences of the catalyst system on the morphology, structure and conductivity of a new type of polyacetylene. Makromol Chem Macromol Symp 24:115–128

    Article  Google Scholar 

  88. Schimmel T, Denninger G, Riess W, Voit J, Schwoerer M, Schoepe W, Naarmann H (1989) High-σ polyacetylene: DC conductivity between 14 mK and 300 K. Synth Metals 28:D11–D18

    Article  CAS  Google Scholar 

  89. Winter H, Sachs G, Dormann E, Cosmo R, Naarmann H (1990) Magnetic properties of spin-labelled polyacetylene. Synth Metals 36:353–365

    Article  CAS  Google Scholar 

  90. Schimmel Th, Schwoerer M, Naarmann H (1990) Mechanisms limiting the D.C. conductivity of high-conductivity polyacetylene. Synth Metals 37:1–6

    Article  CAS  Google Scholar 

  91. Schimmel T, Glaser M, Schwoerer M, Naarmann H (1991) Conductivity barriers and transmission electron microscopy on highly conducting polyacetylene. Synth Metels 41–43:19–25

    Article  Google Scholar 

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  1. Department of Chemistry and Biochemistry, North Dakota State University, Fargo, ND, USA

    Seth C. Rasmussen

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Rasmussen, S.C. (2018). Doped Polyacetylene. In: Acetylene and Its Polymers. SpringerBriefs in Molecular Science(). Springer, Cham. https://doi.org/10.1007/978-3-319-95489-9_6

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