Photophysical and theoretical investigations of oligo(p-phenyleneethynylene)s: effect of alkoxy substitution and alkyne-aryl bond rotations.
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 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, confirming the existence of a single emitting species.
James
P V
PV
Photosciences and Photonics, Chemical Sciences Division, Regional Research Laboratory (CSIR), Trivandrum 695 019 India.
Sudeep
P K
PK
Suresh
C H
CH
Thomas
K George
KG
D000085:Acetates / Q000737:chemistry; D000478:Alkylation; D000480:Alkynes / Q000737:chemistry*; D004987:Ethers / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010777:Photochemistry; D012399:Rotation; D013056:Spectrophotometry, Ultraviolet; D055672:Static Electricity
D000085:Acetates; D000480:Alkynes; D004987:Ethers; C436384:phenyleneethynylene