Aromatic-bridged and meso-meso-linked BF₂-smaragdyrin dimers exhibit fast decays in polar solvents by symmetry-breaking charge transfer.

ABSTRACT: Symmetry-breaking charge transfer is one of the key process in photosynthetic reaction centers and specific artificial optoelectronic devices such as dye-sensitized solar cells. Here we report the synthesis of aromatic-bridged BF₂-smaragdyrin dimers, meso-free BF₂-smaragdyrin, and its meso-meso-linked BF₂-smaragdyrin dimer. The decays of S₁-states of these dimers are accelerated with an increase in solvent polarity and a decrease in the distance between the two BF₂-smaragdyrin units, suggesting symmetry-breaking charge transfer. The fluorescence lifetimes of the dimers become shortened in polar solvents. However, ultrafast transient absorption spectroscopy do not detect charge-separated ion pairs. On the basis of these results, we conclude that the decays of the excited states of the BF₂-smaragdyrin dimers are accelerated by solvation-induced symmetry-breaking charge transfer, depending on the degree of the electronic interaction between the smaragdryin units as a rare case for porphyrinoids. The degree of charge transfer is larger for dimers with larger electronic interactions.

SUBMITTER: Wen L 

PROVIDER: S-EPMC9911704 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature