Abstract
Three anthracene (An)-naphthalenediimide (NDI) compact electron donor-acceptor dyads were prepared. Femtosecond transient absorption (fs-TA) spectra show fast charge separation (ca. 0.9-1.7 ps) and relatively slow charge recombination (ca. 8-565 ps) upon photoexcitation; moreover, the (3)An state was observed for 9-An-NDI, whereas the final state is (NDI)-N-3 for both 9-An-Ph-NDI and 2-An-Ph-NDI, ...
Abstract
Three anthracene (An)-naphthalenediimide (NDI) compact electron donor-acceptor dyads were prepared. Femtosecond transient absorption (fs-TA) spectra show fast charge separation (ca. 0.9-1.7 ps) and relatively slow charge recombination (ca. 8-565 ps) upon photoexcitation; moreover, the (3)An state was observed for 9-An-NDI, whereas the final state is (NDI)-N-3 for both 9-An-Ph-NDI and 2-An-Ph-NDI, which have an intervening phenyl linker between the An and NDI units. Nanosecond transient absorption (ns-TA) spectra indicate that the lowest triplet state of all the dyads is (3)An, with triplet lifetimes of 139-354 mu s. An unusually slow intramolecular triplet-triplet energy transfer (TTET) was observed for 9-An-Ph-NDI and 2-An-Ph-NDI (32-85 ns). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy confirms that the intersystem crossing (ISC) mechanism is spin orbit charge transfer ISC (SOCT-ISC) for all the dyads; for 9-An-NDI, only the (3)An state was observed, while for the other two dyads, both (NDI)-N-3 and (3)An states were observed, with their relative population changing with increasing delay time, which supports TTET.
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