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

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, phi(Delta)=86 %) as compared with PBI-2-AN (phi(Delta)=57 %), which has a more coplanar geometry. By nanosecond transient absorption spectroscopy, a long-lived PBI localized triplet state was observed (tau(T)=139 mu s). 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.

Automated summary

The study investigated the impact of spin-orbit charge transfer intersystem crossing on PBI-AN donor-acceptor dyads/triad, revealing that molecular conformation, electronic coupling, and dihedral angle between donor and acceptor significantly affect photophysical properties. The dyad PBI-9-AN with orthogonal geometry showed low ground-state coupling and efficient intersystem crossing, while the more coplanar PBI-2-AN exhibited weaker performance in these aspects.