Polymer Bulletin

, Volume 69, Issue 2, pp 137–147 | Cite as

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Original Paper

Abstract

Electron-rich, side chain alkynes of an aromatic polyamine were functionalized by a [2+2] cycloaddition, followed by retro-cyclization with the electron-accepting 7,7,8,8-tetracyanoquinodimethane (TCNQ). 1H NMR studies were used to optimize the reaction conditions. Mild heating to >50 °C afforded the postfunctionalized aromatic polyamines with the desired acceptor amounts. The quantitative TCNQ addition was demonstrated by the MALDI-TOF mass spectrum and elemental analysis. Introduction of the cyano-based acceptor moieties into the polymer side chains resulted in unusually strong intermolecular interactions. In addition to the π–π interactions of the extended acceptor moieties, these intermolecular forces were supposed to improve the thermal stability of the aromatic polymers. Furthermore, the donor–acceptor chromophores formed by this postfunctionalization displayed low energy charge-transfer bands and redox activities in both the anodic and cathodic directions. The straightforward postfunctionalization technique using the alkyne–TCNQ addition is useful for the preparation of narrow band gap polymers in one step.

Keywords

Aromatic polyamine Charge transfer Electrochemistry Postfunctionalization 

References

  1. 1.
    Heeger AJ (2010) Semiconducting polymers: the third generation. Chem Soc Rev 39:2354–2371CrossRefGoogle Scholar
  2. 2.
    Shirota Y, Kageyama H (2007) Charge carrier transporting molecular materials and their applications in devices. Chem Rev 107:953–1010CrossRefGoogle Scholar
  3. 3.
    Pu YJ, Soma M, Kido J, Nishide H (2001) A novel triphenylamine-substituted poly(p-phenylenevinylene): improved photo- and electroluminescence properties. Chem Mater 13:3817–3819CrossRefGoogle Scholar
  4. 4.
    Michinobu T, Kumazawa H, Otsuki E, Usui H, Shigehara K (2009) Synthesis and properties of nitrogen-linked poly(2,7-carbazole)s as hole-transport material for organic light emitting diodes. J Polym Sci Part A Polym Chem 47:3880–3891CrossRefGoogle Scholar
  5. 5.
    Yokozawa T, Yokoyama A (2009) Chain-growth condensation polymerization for the synthesis of well-defined condensation polymers and π-conjugated polymers. Chem Rev 109:5595–5619CrossRefGoogle Scholar
  6. 6.
    Osaka I, McCullough RD (2008) Advances in molecular design and synthesis of regioregular polythiophenes. Acc Chem Res 41:1202–1214CrossRefGoogle Scholar
  7. 7.
    Zaumseil J, Sirringhaus H (2007) Electron and ambipolar transport in organic field-effect transistors. Chem Rev 107:1296–1323CrossRefGoogle Scholar
  8. 8.
    Tsuchiya K, Sakakura T, Ogino K (2011) Synthesis of triphenylamine copolymers and effect of their chemical structures on physical properties. Macromolecules 44:5200–5208CrossRefGoogle Scholar
  9. 9.
    Michinobu T, Okoshi K, Osako H, Kumazawa H, Shigehara K (2008) Band-gap tuning of carbazole-containing donor-acceptor type conjugated polymers by acceptor moieties and π-spacer groups. Polymer 49:192–199CrossRefGoogle Scholar
  10. 10.
    Michinobu T, Osako H, Murata K, Shigehara K (2010) Blue, green, and red light emission of 1,8-carbazole-based conjugated polymers. Chem Lett 39:168–169CrossRefGoogle Scholar
  11. 11.
    Babel A, Jenekhe S (2003) High electron mobility in ladder polymer field-effect transistors. J Am Chem Soc 125:13656–13657CrossRefGoogle Scholar
  12. 12.
    Letizia JA, Salata MR, Tribout CM, Facchetti A, Ratner MA, Marks TJ (2008) n-Channel polymers by design: optimizing the interplay of solubilizing substituents, crystal packing, and field-effect transistor characteristics in polymeric bithiophene-imide semiconductors. J Am Chem Soc 130:9679CrossRefGoogle Scholar
  13. 13.
    Michinobu T (2010) Click synthesis of donor-acceptor-type aromatic polymers. Pure Appl Chem 82:1001–1009CrossRefGoogle Scholar
  14. 14.
    Michinobu T (2011) Adapting semiconducting polymer doping techniques to create new types of click postfunctionalization. Chem Soc Rev 40:2306–2316CrossRefGoogle Scholar
  15. 15.
    Michinobu T, Kumazawa H, Noguchi K, Shigehara K (2009) One-step synthesis of donor-acceptor type conjugated polymers from ferrocene-containing poly(aryleneethynylene)s. Macromolecules 42:5903–5905CrossRefGoogle Scholar
  16. 16.
    Michinobu T, Fujita H (2010) Postfunctionalization of alkyne-linked conjugated carbazole polymer by thermal addition reaction of tetracyanoethylene. Materials 3:4773–4783CrossRefGoogle Scholar
  17. 17.
    Li Y, Hyakutake T, Michinobu T (2011) Oxygen permeability change of polyphenylacetylene derivatives by postfunctional TCNE addition. Chem Lett 40:570–572CrossRefGoogle Scholar
  18. 18.
    Wang D, Michinobu T (2011) One-step synthesis of ladder-type fused poly(benzopentalene) derivatives with tunable energy levels by variable substituents. J Polym Sci A Polym Chem 49:72–81CrossRefGoogle Scholar
  19. 19.
    Yuan Y, Michinobu T (2011) Microwave-assisted TCNE/TCNQ addition to poly(thienyleneethynylene) derivative for construction of donor-acceptor chromophores. J Polym Sci A Polym Chem 49:1013–1020CrossRefGoogle Scholar
  20. 20.
    Fujita H, Tsuboi K, Michinobu T (2011) High-yielding alkyne–tetracyanoethylene addition reactions: a powerful tool for analyzing alkyne-linked conjugated polymer structures. Macromol Chem Phys 212:1758–1766CrossRefGoogle Scholar
  21. 21.
    Michinobu T, May JC, Lim JH, Boudon C, Gisselbrecht JP, Seiler P, Gross M, Biaggio I, Diederich F (2005) A new class of organic donor–acceptor molecules with large third-order optical nonlinearities. Chem Commun 737–739Google Scholar
  22. 22.
    Michinobu T, Boudon C, Gisselbrecht JP, Seiler P, Frank B, Moonen NNP, Gross M, Diederich F (2006) Donor-substituted 1,1,4,4-tetracyanobutadienes (TCBDs): new chromophores with efficient intramolecular charge-transfer interactions by atom-economic synthesis. Chem Eur J 12:1889–1905CrossRefGoogle Scholar
  23. 23.
    Kolb HC, Finn MG, Sharpless KB (2001) Click chemistry: diverse chemical function from a few good reactions. Angew Chem Int Ed 40:2004–2021CrossRefGoogle Scholar
  24. 24.
    Michinobu T (2008) Click-type reaction of aromatic polyamines for improvement of thermal and optoelectronic properties. J Am Chem Soc 130:14074–14075CrossRefGoogle Scholar
  25. 25.
    Yuan Y, Michinobu T (2011) Energy level tuning of polythiophene derivative by click chemistry-type postfunctionalization of side chain alkynes. J Polym Sci A Polym Chem 49:225–233CrossRefGoogle Scholar
  26. 26.
    Onuma KI, Kai Y, Yasuoka N, Kasai N (1975) The crystal and molecular structure of trans-bis(trimethylphosphine)propynyl-1-(4′-dicyanomethylene-cyclohexa-2′,5′-dien-1-yliden)-3,3-dicyano-2-methyl-prop-2-en-1-ylplatinum, a reaction product of trans-bis(trimethylphosphine)bis(propynyl)platinum and 7,7,8,8-tetracyanoquinodimethane. Bull Chem Soc Jpn 48:1696–1700CrossRefGoogle Scholar
  27. 27.
    Kivala M, Boudon C, Gisselbrecht JP, Seiler P, Gross M, Diederich F (2007) A novel reaction of 7,7,8,8-tetracyanoquinodimethane (TCNQ): charge-transfer chromophores by [2+2] cycloaddition with alkynes. Chem Commun 4731–4733Google Scholar
  28. 28.
    Reutenauer P, Kivala M, Jarowski PD, Boudon C, Gisselbrecht JP, Gross M, Diederich F (2007) New strong organic acceptors by cycloaddition of TCNE and TCNQ to donor-substituted cyanoalkynes. Chem Commun 4898–4900Google Scholar
  29. 29.
    Butler P, Manning AR, AcAdam CJ, Simpson J (2008) The reactions of some σ-alkynylnickel complexes with 7,7,8,8-tetracyanoquinodimethane. J Organomet Chem 693:381–392CrossRefGoogle Scholar
  30. 30.
    Bruce MI, Cole MI, Parker CR, Skelton BW, White AH (2008) Synthesis and some reactions of the heterometallic C7 complex Cp*(dppe)Ru C≡CC≡CC≡CC{Co3(μ-dppm)(CO)7}. Organometallics 27:3352–3367CrossRefGoogle Scholar
  31. 31.
    Kivala M, Boudon C, Gisselbrecht JP, Enko B, Seiler P, Müller IB, Langer N, Jarowski PD, Gescheidt G, Diederich F (2009) Organic super-acceptors with efficient intramolecular charge-transfer interactions by [2+2] cycloadditions of TCNE, TCNQ, and F4-TCNQ to donor-substituted cyanoalkynes. Chem Eur J 15:4111–4123CrossRefGoogle Scholar
  32. 32.
    Washino Y, Tsuboi K, Michinobu T (2011) Simultaneous formation of donor-acceptor chromophores and cross-linking for electro-optic polymer materials. J Photopolym Sci Technol 24:305–309CrossRefGoogle Scholar
  33. 33.
    Washino Y, Michinobu T (2011) Application of alkyne–TCNQ addition reaction to polymerization. Macromol Rapid Commun 32:644–648CrossRefGoogle Scholar
  34. 34.
    Washino Y, Murata K, Ashizawa M, Kawauchi S, Michinobu T (2011) Creation of persistent charge-transfer interactions in TCNQ polyester. Polym J 43:364–369CrossRefGoogle Scholar
  35. 35.
    Li Y, Tsuboi K, Michinobu T, Ishida Y, Hirai T, Hayakawa T, Kakimoto MA (2010) Efficient synthesis of block copolymers bearing donor-acceptor chromophores for second-order nonlinear optical applications. J Photopolym Sci Technol 23:337–342CrossRefGoogle Scholar
  36. 36.
    Li Y, Michinobu T (2010) Sequential double click reactions: a highly efficient post-functionalization method for optoelectronic polymers. Polym Chem 1:72–74CrossRefGoogle Scholar
  37. 37.
    Li Y, Tsuboi K, Michinobu T (2010) Double click synthesis and second-order nonlinearities of polystyrenes bearing donor–acceptor chromophores. Macromolecules 42:5277–5286CrossRefGoogle Scholar
  38. 38.
    Hamciuc E, Hamciuc C, Cazacu M, Ignat M, Zarnescu G (2009) Polyimide–polydimethylsiloxane copolymers containing nitrile groups. Eur Poly J 45:182–190CrossRefGoogle Scholar
  39. 39.
    Kato SI, Diederich F (2010) Non-planar push–pull chromophores. Chem Commun 46:1994–2006CrossRefGoogle Scholar
  40. 40.
    Morimoto M, Murata K, Michinobu T (2011) Photochemical control of a highly efficient addition reaction between electron-rich alkynes and tetracyanoethylene. Chem Commun 47:9819–9821CrossRefGoogle Scholar
  41. 41.
    Esembeson B, Scimeca ML, Michinobu T, Diederich F, Biaggio I (2008) A high-optical quality supramolecular assembly for third-order integrated nonlinear optics. Adv Mater 20:4584–4587CrossRefGoogle Scholar
  42. 42.
    Kato SI, Kivala M, Schweizer WB, Boudon C, Gisselbrecht JP, Diederich F (2009) Origin of intense intramolecular charge-transfer interactions in nonplanar push–pull chromophores. Chem Eur J 15:8687–8691CrossRefGoogle Scholar
  43. 43.
    Jordan M, Kivala M, Boudon C, Gisselbrecht JP, Schweizer WB, Seiler P, Diederich F (2011) Switching the regioselectivity in cycloaddition-retro-electrocyclizations between donor-activated alkynes and the electron-accepting olefins TCNE and TCNQ. Chem Asian J 6:396–401CrossRefGoogle Scholar
  44. 44.
    Tang X, Liu W, Wu J, Lee CS, You J, Wang P (2010) Synthesis, crystal structures, and photophysical properties of triphenylamine-based multicyano derivatives. J Org Chem 75:7273–7278CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Yusuke Washino
    • 1
  • Kimie Murata
    • 2
  • Tsuyoshi Michinobu
    • 2
    • 3
  1. 1.Department of Organic and Polymeric MaterialsTokyo Institute of TechnologyTokyoJapan
  2. 2.Global Edge InstituteTokyo Institute of TechnologyTokyoJapan
  3. 3.PRESTO, Japan Science and Technology Agency (JST)KawaguchiJapan

Personalised recommendations