Synthesis, self-assembly, and photophysical properties of cationic oligo(p-phenyleneethynylene)s
© 2011 American Chemical Society
| Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1999. - 27(2011), 8 vom: 19. Apr., Seite 4945-55 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2011
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| Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
| Schlagworte: | Journal Article Research Support, U.S. Gov't, Non-P.H.S. Alkynes Cations Ethers Phosphates phenyleneethynylene sodium polymetaphosphate P1BM4ZH95L |
| Zusammenfassung: | © 2011 American Chemical Society Three series of cationic oligo p-phenyleneethynylenes (OPEs) have been synthesized to study their structure-property relationships and gain insights into the transition from molecular to macromolecular properties. The absorbance maxima and molar extinction coefficients in all three sets increase with increasing number of repeat units; however, the increase in λ(max) between the oligomers having 2 and 3 repeat units is very small, and the oligomer having 3 repeat units shows virtually the same spectra as a p-phenyleneethynylene polymer having 49 repeat units. A computational study of the oligomers using density functional theory calculations indicates that while the simplest oligomers (OPE-1) are fully conjugated, the larger oligomers are nonplanar and the limiting "segment chromophore" may be confined to a near-planar segment extending over three or four phenyl rings. Several of the OPEs self-assemble on anionic "scaffolds", with pronounced changes in absorption and fluorescence. Both experimental and computational results suggest that the planarization of discrete conjugated segments along the phenylene-ethynylene backbone is predominantly responsible for the photophysical characteristics of the assemblies formed from the larger oligomers. The striking differences in fluorescence between methanol and water are attributed to reversible nucleophilic attack of structured interfacial water on the excited singlet state |
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| Beschreibung: | Date Completed 26.08.2011 Date Revised 19.11.2015 published: Print-Electronic Citation Status MEDLINE |
| ISSN: | 1520-5827 |
| DOI: | 10.1021/la1050173 |