Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer - Effect of Photochemical Trans-Cis Isomerization

Photoinduced charge transfer and separation events in a newly synthesized azobenzene-bridged perylenediimide-dimer (PDI-dimer) are demonstrated. Trans-to-cis conversion (similar to 50 % efficiency) from the initial trans PDI-dimer by 355 nm pulsed laser light, and its reversal, cis-to-trans, process by 435 nm laser light irradiation has been possible to accomplish. Efficient fluorescence quenching in the PDI-dimer, more so for the cis isomer was witnessed, and such quenching increased with increasing solvent polarity. DFT-calculated geometry and electronic structures helped in visualizing the charge transfer in the PDI-dimer in both isomeric forms, and also revealed certain degree of participation of the azobenzene entity in the charge transfer events. Femtosecond transient absorption spectral studies confirmed occurrence of both charge transfer followed by charge separation in the studied PDI-dimer in both trans and cis forms in polar solvents, and the evaluated time constants from Global target analysis revealed accelerated events in the cis PDI-dimer due to proximity effects. The present study offers key insights on the role of the azobenzene bridge, and the dimer geometry in governing the excited state charge transfer and separation in symmetrically linked PDI dimer.

Automated summary

The study demonstrates photoinduced charge transfer and separation events in a newly synthesized azobenzene-bridged perylenediimide-dimer (PDI-dimer). The fluorescence quenching in the PDI-dimer, especially for the cis isomer, was found to increase with increasing solvent polarity. DFT calculations helped visualize the charge transfer in the PDI-dimer and revealed the involvement of the azobenzene entity in the charge transfer events.