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Journal of Physical Chemistry B, Vol.107, No.25, 6019-6021, 2003
Excitonic coupling between B and Q transitions in a porphyrin aggregate
Aggregation distinctively changes the absorption and fluorescence anisotropy spectrum of beta-tetraethyl-tetrapyridinyl-porphyrin 1. A large excitonic splitting of the B band occurs, and the Q band absorption is distinctively enhanced. The latter effect must be attributed to intensity transfer from the B- to the Q-band region that is mediated by an excitonic coupling between B and Q transition dipoles. In the fluorescence anisotropy spectrum of the aggregate of 1, all Q bands and the red-shifted B band are polarized parallel, reflecting the strong interband excitonic coupling. A qualitative explanation of the observed excitonic effects is given.