Charge Separation/Recombination, Intersystem Crossing, and Unusually Slow Intramolecular Triplet–Triplet Energy Transfer in Naphthalenediimide–Anthracene Compact Energy Donor–Acceptor Dyads
Xi Chen, А. А. Суханов, Maria Letizia Taddei, Bernhard Dick, Jianzhang Zhao, Violeta K. Voronkova, Mariangela Di Donato
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 3An state was observed for 9-An-NDI, whereas the final state is 3NDI 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 3An, with triplet lifetimes of 139–354 μs. 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 3An state was observed, while for the other two dyads, both 3NDI and 3An states were observed, with their relative population changing with increasing delay time, which supports TTET.