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Spin–Orbit Charge‐Transfer Intersystem Crossing in Anthracene–Perylenebisimide Compact Electron Donor–Acceptor Dyads and Triads and Photochemical Dianion Formation
Author(s) -
Rehmat Noreen,
Kurganskii Ivan V.,
Mahmood Zafar,
Guan Qing Lin,
Zhao Jianzhang,
Xing Yong Heng,
Gurzadyan Gagik G.,
Fedin Matvey V.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202005285
Subject(s) - intersystem crossing , photochemistry , photoexcitation , chemistry , acceptor , ultrafast laser spectroscopy , triplet state , ground state , chromophore , electron donor , dihedral angle , spectroscopy , excited state , singlet state , atomic physics , molecule , hydrogen bond , condensed matter physics , catalysis , biochemistry , physics , organic chemistry , quantum mechanics
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, Φ Δ =86 %) as compared with PBI‐2‐AN ( Φ Δ =57 %), which has a more coplanar geometry. By nanosecond transient absorption spectroscopy, a long‐lived PBI localized triplet state was observed ( τ T =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 ( PBI 2− ) 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 PBI 2− .