Spin–Orbit Charge‐Transfer Intersystem Crossing in Anthracene–Perylenebisimide Compact Electron Donor–Acceptor Dyads and Triads and Photochemical Dianion Formation.

Rehmat, Noreen; Kurganskii, Ivan V.; Mahmood, Zafar; Guan, Qing Lin; Zhao, Jianzhang; Xing, Yong Heng; Gurzadyan, Gagik G.; Fedin, Matvey V.

Perylenebisimide (PBI)–anthracene (AN) donor–acceptor dyads/triad were prepared to investigate spin–orbit charge‐transfer intersystem crossing (SOCT‐ISC). Molecular conformation was controlled by connecting PBI units to the 2‐ or 9‐position of the AN moiety. Steady‐state, time‐resolved transient absorption and emission spectroscopy revealed that chromophore orientation, electronic coupling, and dihedral angle between donor and acceptor exert a significant effect on the photophysical property. The dyad PBI‐9‐AN with orthogonal geometry shows weak ground‐state coupling and efficient intersystem crossing (ISC, ΦΔ=86 %) as compared with PBI‐2‐AN (ΦΔ=57 %), which has a more coplanar geometry. By nanosecond transient absorption spectroscopy, a long‐lived PBI localized triplet state was observed (τT=139 μs). Time‐resolved EPR spectroscopy demonstrated that the electron spin polarization pattern of the triplet state is sensitive to the geometry and number of AN units attached to PBI. Reversible and stepwise generation of near‐IR‐absorbing PBI radical anion (PBI−⋅) and dianion (PBI2−) was observed on photoexcitation in the presence of triethanolamine, and it was confirmed that selective photoexcitation at the near‐IR absorption bands of PBI.− is unable to produce PBI2−.

DIANIONS; ELECTRON spin; ELECTRON paramagnetic resonance spectroscopy; MOLECULAR conformation; DYADS; TIME-resolved spectroscopy; ELECTRON spin states; RADICAL anions

Chemistry - A European Journal, 2021, Vol 27, Issue 17, p5521

0947-6539

Academic Journal

10.1002/chem.202005285