Abstract

The effect of pressure on the photodynamics of intramolecular electron transfer has been examined using picosecond time-resolved and steady- state fluorescence spectroscopy. Two supramolecuiar systems were studied containing two chromophores connected by a rigid molecular bridge. The rigidity of these molecules enable them to remain at a well defined separation and orientation, making them insensitive to any conformational change as the pressure is increased. The molecules under examination were dimethoxynaphthalene-{polynorbornyl (8,σ-bonds)}- dicyanovinyl (DMN[8]DCV) and N.N-dimethylaniline- {polynorbornyl (4,σ-bonds)}-dimethoxynaphthalene (DMA [4] DMN [2] ). The energetics for electron transfer in these molecules differ significantly, providing insight into the effects of solvent on the photodynamics of electron transfer.

© 1996 Optical Society of America