Kaur, Irvinder and Jia, WL and Kopreski, RP and Selvarasah, S and Dokmeci, MR and Pramanik, C and McGruer, NE and Miller, GP. (2008) Substituent Effects in Pentacenes: Gaining Control over HOMO−LUMO Gaps and Photooxidative Resistances. Journal of the American Chemical Society, 130 (48). p. 16274. ISSN 00027863
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A combined experimental and computational study of a series of substituted pentacenes including halogenated, phenylated, silylethynylated and thiolated derivatives is presented. Experimental studies include the synthesis and characterization of six new and six known pentacene derivatives and a kinetic study of each derivative under identical photooxiclative conditions. Structures, HOMO-LUMO energies and associated gaps were calculated at the B3LYP/6-311+G**//PM3 level while optical and electrochemical HOMO-LUMO gaps were measured experimentally. The combined results provide for the first time a quantitative assessment of HOMO-LUMO gaps and photooxiclative resistances for a large series of pentacene derivatives as a function of substituents. The persistence of each pentacene derivative is impacted by a combination of steric resistance and electronic effects as well as the positional location of each substituent. Silylethynyl-substituted pentacenes like TIPS-pentacene possess small HOMO-LUMO gaps but are not the longest lived species under photooxiclative conditions, contrary to popular perception. A pentacene derivative with both chlorine substituents in the 2,3,9,10 positions and o-alkylphenyl substituents in the 6,13 positions is longer lived than TIPS-pentacene. Of all the derivatives studied, alkylthio- and arylthio-substituted pentacenes are most resistant to photooxidation, possess relatively small HOMO-LUMO gaps and are highly soluble in a variety of organic solvents. These results have broad implications for the field of organic molecular electronics where OFET, OLED, and other applications can benefit from highly persistent, solution processable pentacene derivatives.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | FIELD-EFFECT TRANSISTORS; LIGHT-EMITTING-DIODES; DIELS-ALDER REACTIONS; THIN-FILM-TRANSISTOR; FUNCTIONALIZED PENTACENE; ORGANIC SEMICONDUCTORS; 6,13-DISUBSTITUTED PENTACENES; PHOTOSENSITIZED OXIDATION; ELECTRONIC-PROPERTIES; SINGLET OXYGEN |
| InterNano Taxonomy: | Nanomanufacturing Characterization Techniques |
| Collections: | Nanomanufacturing Research Collection |
| Depositing User: | Danielle Federa |
| Date Deposited: | 17 Jun 2009 16:24 |
| Last Modified: | 17 Jun 2009 16:24 |
| URI: | http://eprints.internano.org/id/eprint/124 |
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