{Reference Type}: Journal Article
{Title}: Efficient Spin-Orbit Charge-Transfer Intersystem Crossing and Slow Intramolecular Triplet-Triplet Energy Transfer in Bodipy-Perylenebisimide Compact Dyads and Triads.
{Author}: Chen X;Rehmat N;Kurganskii IV;Maity P;Elmali A;Zhao J;Karatay A;Mohammed OF;Fedin MV;
{Journal}: Chemistry
{Volume}: 29
{Issue}: 61
{Year}: 2023 Nov 2
{Factor}: 5.02
{DOI}: 10.1002/chem.202302137
{Abstract}: Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad were prepared to study the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). For BDP-PBI-3, in which BDP was attached at the imide position of PBI, higher singlet oxygen quantum yield (ΦΔ =85 %) was observed than the bay-substituted derivative BDP-PBI-1 (ΦΔ =30 %). Femtosecond transient absorption spectra indicate slow Förster resonance energy transfer (FRET; 40.4 ps) and charge separation (CS; 1.55 ns) in BDP-PBI-3, while for BDP-PBI-1, CS takes 2.8 ps. For triad BDP-PBI-2, ultrafast FRET (149 fs) and CS (4.7 ps) process were observed, the subsequent charge recombination (CR) takes 5.8 ns and long-lived 3 PBI* (179.8 μs) state is populated. Nanosecond transient absorption spectra of BDP-PBI-3 show that the CR gives upper triplet excited state (3 BDP*) and subsequently, via a slow intramolecular triplet energy transfer (14.5 μs), the 3 PBI* state is finally populated, indicating that upper triplet state is involved in SOCT-ISC. Time-resolved electron paramagnetic resonance spectroscopy revealed that both radical pair ISC (RP ISC) and SOCT-ISC contribute to the ISC. A rare electron spin polarization of (e, e, e, e, e, e) was observed for the triplet state formed via the RP ISC mechanism, due to the S-T+1 /T0 states mixing.