Journal of Physical Chemistry, Vol.100, No.32, 13867-13873, 1996
Spectral and Photophysical Properties of Ethylene-Bridged Side-to-Side Porphyrin Dimers .2. Femtosecond Transient Absorption and Picosecond Fluorescence Study of Trans-1,2-bis(Meso-Octaethylporphyrinyl)Ethene
Femtosecond transient absorption and picosecond fluorescence spectra and kinetics have been measured for an ethylene-bridged porphyrin dimer molecule, trans-1,2-bis(meso-octaethylporphyrinyl)ethene (tbis=OEP). In part 1 of this work it was shown with the help of absorption and fluorescence spectroscopy that in solution the molecule exists in at least two different conformers, the P conformer with porphyrin-type spectral properties and the U conformer with spectral properties atypical for porphyrin molecules. As our quantum chemical calculations showed, the U conformer is characterized by a common pi-conjugation through the double-bond bridge. In the present work we have found that the lifetimes of the lowest excited singlet states of the P and U conformers are extraordinary short, similar to 6 ps for P and similar to 7-9 ps for U in toluene at room temperature. Singlet-state lifetimes of both conformers were found to be strongly dependent on solvent viscosity with that of the U-form exhibiting the most pronounced dependence; a fluorescence lifetime of approximately 460 ps was measured for the U conformer in a frozen toluene solution at 77 K. Photoisomerization-like conformational relaxation in the S-1 state, leading the system to the "point of funnel" characterized by decreased Delta E(S-1-S-0) energy gap, is proposed as a mechanism to explain the photophysics of the P and U conformers.
Keywords:SYMMETRIC CHLOROPHYLL DIMER;SANDWICH COMPLEXES;OPTICAL-PROPERTIES;FIXED-DISTANCE;PHOTOISOMERIZATION;MOLECULES;DYNAMICS;STATES;ISOMERIZATION;DEACTIVATION