Photophysical and theoretical investigations of oligo(p-phenyleneethynylene)s: effect of alkoxy substitution and alkyne-aryl bond rotations

James, P. V. ; Sudeep, P. K. ; Suresh, C. H. ; George Thomas, K. (2006) Photophysical and theoretical investigations of oligo(p-phenyleneethynylene)s: effect of alkoxy substitution and alkyne-aryl bond rotations The Journal of Physical Chemistry A, 110 (13). pp. 4329-4337. ISSN 1089-5639

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jp055184o

Related URL: http://dx.doi.org/10.1021/jp055184o

Abstract

The unique photophysical, conformational, and electronic properties of two model phenyleneethynylene-based rigid rod molecular systems, possessing dialkoxy substitutions, are reported in comparison with an unsubstituted system. Twisting of the phenyl rings along the carbon-carbon triple bond is almost frictionless in these systems giving rise to planar as well as several twisted ground-state conformations, and this results in broad structureless absorption in the spectral region of 250-450 nm. In the case of 1,4-bis(phenylethynyl)benzene, a broad absorption band was observed due to the HOMO-LUMO transition, whereas dialkoxy-substituted compounds possess two well-separated bands. Dialkoxy substitution in the 2,5-position of the phenyl ring in phenyleneethynylenes alters its central arene π-orbitals through the resonance interaction with oxygen lone pairs resulting in similar orbital features for HOMO and HOMO-1/HOMO-2. Electronic transition from the low-lying HOMO-1/HOMO-2 orbital to LUMO results in the high-energy band, and the red-shifted band originates from the HOMO-LUMO transition. The first excited-state transition energies at different dihedral angles, calculated by the TDDFT method, indicate that the orthogonal conformation has the highest excitation energy with an energy difference of 15 kcal/mol higher than the low-lying planar conformation. The emission of these compounds originates preferentially from the more relaxed planar conformation resulting in well-defined vibronic features. The fluorescence spectral profile and lifetimes were found to be independent of excitation wavelengths, confirming the existence of a single emitting species.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:51404
Deposited On:28 Jul 2011 11:46
Last Modified:28 Jul 2011 11:46

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