Engineering the Charge-Transfer State to Facilitate Spin–Orbit Charge Transfer Intersystem Crossing in Spirobis[anthracene]diones

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 7.8×10⁸ s⁻¹ to 1.0×10¹¹ 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.