Ultrafast Excited-State Energy Migration Dynamics in an Efficient Light-Harvesting Antenna Polymer Based on Ru(II) and Os(II) Polypyridyl Complexes

A detailed study of the excited state energy migration dynamics that take place within an assembly of Ru(II) and Os(II) polypyridyl complexes linked together through a polymer backbone is presented. The energy migration process is initiated by the photoexcitation of the metal-to-ligand charge transfer (MLCT) transition in one of the Ru(II) complexes and terminated by energy transfer to a lower energy Os(II) trap. Energy transfer sensitization of Os(II) can occur in a single step if the excited state is formed adjacent to a trap, or after a series of hops between isoenergetic rutheniums prior to reaching a trap. The dynamics of the energy transfer process are followed by monitoring the growth of Os(II) luminescence at 780 nm. The kinetics of the growth are complex and can be fit by a sum of two exponentials. This kinetic complexity arises both from the presence of a distribution of donor-acceptor distances and the variety of time scales by which Os(II) can be formed. We have augmented the time-resolved experiments with Monte Carlo simulations, which provide insight into the polymer array's structure and at the same time form the basis of a molecular-level description of the energy migration dynamics. The simulations indicate that the most probable Ru-->Os energy transfer time is approximately 400 ps while the time scale for Ru-->Ru hopping is approximately 1-4 ns. The time scale for Ru-->Ru hopping relative to its natural lifetime (1000 ns) suggests that this polymer system could be extended to considerably longer dimensions without an appreciable loss in its overall efficiency.