Oligothiophene Tetracyanobutadienes: Alternative Donor鈭扐cceptor Architectures for Molecular and Polymeric Materials

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• 作者：Ted M. Pappenfus ; Deborah K. Schneiderman ; Juan Casado ; Juan T. L贸pez Navarrete ; M. Carmen Ruiz Delgado ; Gianni Zotti ; Barbara Vercelli ; Matthew D. Lovander ; Lindsay M. Hinkle ; Jon N. Bohnsack ; Kent R. Mann
• 刊名：Chemistry of Materials
• 出版年：2011
• 出版时间：February 8, 2011
• 年：2011
• 卷：23
• 期：3
• 页码：823-831
• 全文大小：979K
• 年卷期：v.23,no.3(February 8, 2011)
• ISSN：1520-5002

文摘

Oligothiophene-substituted 1,1,4,4-tetracyanobutadienes (TCBDs) have been synthesized by [2 + 2] cycloaddition reactions between tetracyanoethylene and oligothiophene alkynes. The TCBD moiety is compared to other electron acceptors attached to dibutylterthiophene including dicyanovinyl (DCV) and tricyanovinyl (TCV). These donor鈭抋cceptor molecules (TCBD-3T, DCV-3T, and TCV-3T) show red-shifted absorption spectra relative to the unsubstituted oligothiophene as a result of intramolecular charge-transfer (ICT). Monosubstituted terthiophenes bearing the electron acceptors show both oxidation and reduction processes as characterized by cyclic voltammetry. Density functional theory (DFT) calculations are used to explain the electronic and redox properties of the materials. Electrochemical oxidation of a bis(terthienyl)-substituted TCBD molecule (3T-TCBD-3T) yields a conducting polymer exhibiting balanced ambipolar redox conduction with similar values for the oxidized and reduced states of the polymer (1 脳 10^鈭? S cm^鈭?). Raman spectra of the asymmetric donor鈭抋cceptor materials are characterized by two intense bands characteristic of the aromatic and quinoidal regions in the conjugated 蟺-system of the oligothiophene.