TY - JOUR

T1 - Efficient Spin Orbit Charge Transfer Intersystem Crossing and Slow Intramolecular Triplet-Triplet Energy Transfer in Bodipy-Perylenebisimide Compact Dyads and Triads

AU - Chen, Xi

AU - Rehmat, Noreen

AU - Kurganskii, Ivan V

AU - Maity, Partha

AU - Elmali, Ayhan

AU - Zhao, Jianzhang

AU - Karatay, Ahmet

AU - Mohammed, Omar F

AU - Fedin, Matvey V

N1 - Acknowledgements: J.Z. thanks the NSFC (U2001222), the Research and Innovation Team Project of Dalian University of Technology (DUT2022TB10), the Fundamental Research Funds for the Central Universities (DUT22LAB610) and the State Key Laboratory of FineChemicals for financial support. M. F. and I. K. thank the Ministry of Science and Higher Education of the Russian Federation (Grant No. 075-15-2020-779). © 2023 Wiley-VCH GmbH.

PY - 2023/11/2

Y1 - 2023/11/2

N2 - We prepared Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad 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 (FD = 85%) was observed than the bay-substituted derivative BDP-PBI-1 (FD = 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 3PBI* (179.8 µs) state is populated. Nanosecond transient absorption spectra of BDP-PBI-3 show that the CR gives upper triplet excited state (3BDP*) and subsequently, via a slow intramolecular triplet energy transfer (14.5 µs), the 3PBI* 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.

AB - We prepared Bodipy (BDP)-perylenebisimide (PBI) donor-acceptor dyads/triad 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 (FD = 85%) was observed than the bay-substituted derivative BDP-PBI-1 (FD = 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 3PBI* (179.8 µs) state is populated. Nanosecond transient absorption spectra of BDP-PBI-3 show that the CR gives upper triplet excited state (3BDP*) and subsequently, via a slow intramolecular triplet energy transfer (14.5 µs), the 3PBI* 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.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85172703667&origin=inward&txGid=9cf607ed67eb7bd0b2a7f4e735474446

UR - https://www.mendeley.com/catalogue/d8c66555-e0d7-3be1-83a4-e9674e58f554/

U2 - 10.1002/chem.202302137

DO - 10.1002/chem.202302137

M3 - Article

C2 - 37553294

VL - 29

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 61

M1 - e202302137

ER -