Modulating Charge Separation and Intersystem Crossing in Donor-Switch-Acceptor Systems: A Computational Study

Charge separation and intersystem crossing play critical roles in various applications of organic long persistent luminescence materials, including light-emitting diodes, chemical sensors, theranostics, and many biomedical and information applications. Using first-principles calculations, we demonstrate that an azobenzene acting as a photoswitch can be used for altering the configuration of a donor-switch-acceptor (D-S-A) molecular system to ensure charge separation and promote intersystem crossing upon photoexcitation. The trans to cis photoisomerization of an azobenzene switch creates an electron trap that stabilizes the charge-separated state. The cis conformation further facilitates the singlet to triplet intersystem crossing in the excited state. Our theoretical study of the D-S-A system may help the design of long persistent luminescent organic devices.