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

被引:142
作者
James, PV
Sudeep, PK
Suresh, CH [1 ]
Thomas, KG
机构
[1] CSIR, Reg Res Lab, Comp Simulat & Modeling Grp, Trivandrum 695019, Kerala, India
[2] CSIR, Reg Res Lab, Div Chem Sci, Trivandrum 695019, Kerala, India
关键词
D O I
10.1021/jp055184o
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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 clue to the HOMO-LUMO transition, whereas dialkoxy-substituted compounds possess two well-separated hands. Dialkoxy substitution in the 2,5-position of the phenyl ring in phenyleneethynylenes alters its central arene pi-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, confinning the existence of a single emitting species.
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页码:4329 / 4337
页数:9
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