Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes
- 194 Downloads
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.
KeywordsAromatic polyamine Charge transfer Electrochemistry Postfunctionalization
This work was supported, in part, by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, Japan.
- 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
- 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.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
- 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.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.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
- 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