The synthesis and photophysical properties of a ruthenium dyad (4) and triad (5) are reported. Both biomimetic
systems are physical models for the photosynthetic reaction center. They consist of a ruthenium(II)-polypyridyl
sensitizer featuring chemically attached 3,3‘-dimethyl-4,4‘-viologen and 4,4‘-viologen electron acceptors. The
binding of the chemically attached electron acceptors by the three structurally different crown ethers, DB30C10,
BBO5O5, and AAO5O5, offers a remarkable tool for the enhancement of the lifetimes of the charge separated
states (τCS), up to a factor of 2 × 104. The drastic increase in the lifetimes observed can be explained by a
decrease in the reorganization energy λ due to the presence of the crown ether units bound to the viologen
acceptor.
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