Click synthesis of donor–acceptor-type aromatic polymers

Michinobu, Tsuyoshi

doi:10.1351/pac-con-09-09-09

Cited by 56 publications

(35 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…11 The chemical reactions include the thermal [2+2] cycloaddition between electron-rich alkynes and electron-deficient ethene moieties of acceptor molecules, such as tetracyanoethylene and TCNQ, followed by ring opening of the cyclobutene intermediates formed, yielding the donor-acceptor chromophores, as exemplified in Scheme 1 (see ref . 12).…”

Section: Introductionmentioning

confidence: 99%

Creation of persistent charge-transfer interactions in TCNQ polyester

Murata

Ashizawa

Kawauchi

et al. 2011

Polym J

Self Cite

View full text Add to dashboard Cite

A 7,7,8,8-tetracyanoquinodimethane polyester was converted into a strongly colored polyester with low-energy charge-transfer (CT) bands by treatment with electron-rich alkyne molecules under mild conditions. The post-functionalization was monitored by its ultraviolet-visible-near infrared (IR) spectra, which suggested a quantitative addition reaction without any side reactions. This result was further supported by 1 H and 13 C nuclear magnetic resonance, IR and elemental analyses. The functionalized polymer retained a high thermal stability with a decomposition onset temperature of B200 1C and B63% residual soot at 500 1C. The CT chromophores in the polymer showed a clear positive solvatochromism and redox behaviors in both anodic and cathodic directions. The HOMO and LUMO levels estimated from the first oxidation potential (E ox,1 ) and the first reduction potential (E red,1 ), respectively, were markedly elevated by this post-functionalization. The extent of HOMO elevation (1.45 eV) was more significant than that of LUMO elevation (0.44 eV).

show abstract

Section: Introductionmentioning

confidence: 99%

Creation of persistent charge-transfer interactions in TCNQ polyester

Murata

Ashizawa

Kawauchi

et al. 2011

Polym J

Self Cite

View full text Add to dashboard Cite

show abstract

“…We have been trying to develop an experimental technique to control the polymer energy levels by adapting semiconducting polymer doping techniques [13][14][15][16][17][18][19][20]. The key reagent of this project is cyano-containing strong acceptor molecules, which are originally p-type doping reagents, but undergo [2?2] cycloaddition with electrondonor-activated alkynes [21,22].…”

Section: Introductionmentioning

confidence: 99%

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

Murata

Michinobu

2011

Polym. Bull.

Self Cite

View full text Add to dashboard Cite

Electron-rich, side chain alkynes of an aromatic polyamine were functionalized by a [2?2] cycloaddition, followed by retro-cyclization with the electronaccepting 7,7,8,8-tetracyanoquinodimethane (TCNQ). 1 H 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 p-p 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.

show abstract

“…[16,46] This result was confirmed even when 10 equiv. [16,46] This result was confirmed even when 10 equiv.…”

Section: Resultsmentioning

confidence: 65%

Reactions of Alkynyl‐ and 1,1′‐Dialkynylferrocenes with Tetracyanoethylene – Unanticipated Addition at the Less Electron‐Rich of Two Triple Bonds

Krauße

Kielmann

et al. 2015

Eur J Org Chem

View full text Add to dashboard Cite

Alkynylferrocenes react with tetracyanoethylene (TCNE) to form 2-ferrocenyl-1,1,4,4-tetracyanobutadienes. These reactions occur under mild reaction conditions in almost quantitative yields if the triple bond is electron-rich. Systems with more than one triple bond, namely, 1,1Ј-dialkynylferrocenes or diynylferrocenes, react once at the more electron-rich triple bond, and the second reaction cannot be achieved, even under more-forcing reaction conditions. For a diyne with the [a]

show abstract

Click synthesis of donor–acceptor-type aromatic polymers

Cited by 56 publications

References 49 publications

Creation of persistent charge-transfer interactions in TCNQ polyester

Creation of persistent charge-transfer interactions in TCNQ polyester

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

Reactions of Alkynyl‐ and 1,1′‐Dialkynylferrocenes with Tetracyanoethylene – Unanticipated Addition at the Less Electron‐Rich of Two Triple Bonds

Contact Info

Product

Resources

About