Exploration of ground and excited electronic states of aromatic and quinoid S,S-dioxide terthiophenes. Complementary systems for enhanced electronic organic materials

Juan Casado, Marek Z. Zgierski, Paul C. Ewbank, Michael W. Burand, Daron E. Janzen, Kent R Mann, Ted M. Pappenfus, Anna Berlin, Ezequiel Pérez-Inestrosa, Rocío Ponce Ortiz, Juan T.López Navarrete

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45 Scopus citations

Abstract

We analyze the electronic and molecular structures for the ground and excited electronic states of aromatic terthiophene (3T), the quinodimethane 3′,4′-dibutyl-5,5″-bis(dicyanomethylene)-5,5″-dihydro-2, 2′:5′,2″-terthiophene (3Q), and isologues with the middle ring S-oxidized (3TO2, 3QO2). These represent extremes of electron rich and deficient ground states, often exhibiting complementary properties. Oxidizing the central sulfur atom affects the molecular structure, electron affinity, and photophysical properties of both π systems. The consequences for 3T include de-aromatization of the central thiophene, red-shifting of the electronic absorption spectrum, and lowering of the reduction potential. The electron deficient quinoid 3QO2 shows an enhancement of electron affinity from reducing the electron-donor ability of sulfur, and a blue-shifting of its electronic absorption spectrum was seen. Fluorescence emission is quenched in the sulfonated terthiophene, and the contrary effect again would be expected upon sulfonation of a quinoid emitter. Raman vibrational spectroscopy, electrochemistry, and UV-vis and fluorescence spectroscopies are analyzed in conjunction with theoretical calculations.

Original languageEnglish (US)
Pages (from-to)10134-10144
Number of pages11
JournalJournal of the American Chemical Society
Volume128
Issue number31
DOIs
StatePublished - Aug 9 2006

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    Casado, J., Zgierski, M. Z., Ewbank, P. C., Burand, M. W., Janzen, D. E., Mann, K. R., Pappenfus, T. M., Berlin, A., Pérez-Inestrosa, E., Ortiz, R. P., & Navarrete, J. T. L. (2006). Exploration of ground and excited electronic states of aromatic and quinoid S,S-dioxide terthiophenes. Complementary systems for enhanced electronic organic materials. Journal of the American Chemical Society, 128(31), 10134-10144. https://doi.org/10.1021/ja061372w