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Engineering the Charge‐Transfer State to Facilitate Spin–Orbit Charge Transfer Intersystem Crossing in Spirobis[anthracene]diones
Author(s) -
Lv Meng,
Yu Yang,
SandovalSalinas María E.,
Xu Jianhua,
Lei Zuhai,
Casanova David,
Yang Youjun,
Chen Jinquan
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202009439
Subject(s) - intersystem crossing , anthracene , charge (physics) , benzophenone , chemistry , photochemistry , chemical physics , materials science , excited state , atomic physics , physics , quantum mechanics , singlet state
Spiro conjugation has been proposed to dictate the efficiency of charge transfer, which could directly affect the spin–orbit charge transfer intersystem crossing (SOCT‐ISC) process. However, this process has yet to be exemplified. Herein, we prepared three spirobis[anthracene]diones, in which two benzophenone moieties are locked in close proximity and differentially functionalized to fine‐tune the charge transfer state. Its feasibility for SOCT‐ISC was theoretically predicted, then experimentally evaluated. Through fine‐tuning the spiro conjugation coupling and varying the solvent dielectric constants, ISC rate constants were engineered to vary in a dynamic range of three orders of magnitude, from 7.8×10 8 s −1 to 1.0×10 11 s −1 , which is the highest ISC rate reported for SOCT‐ISC system to our knowledge. Our findings substantiate the key factors for effective SOCT‐ISC and offer a new avenue for the rational design of heavy atom free triplet sensitizers.