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

Título :
Excited State Charge Separation in an Azobenzene-Bridged Perylenediimide Dimer – Effect of Photochemical Trans-Cis Isomerization
Autor :
Zink Lorre, Nathalie  
Seetharaman, Sairaman
Gutiérrez Moreno, David
Fernández Lázaro, Fernando
Karr, Paul A.
D’Souza, Francis
Editor :
Wiley-VCH GmbH
Departamento:
Departamentos de la UMH::Farmacología, Pediatría y Química Orgánica
Fecha de publicación:
2021
URI :
https://hdl.handle.net/11000/31033
Resumen :
Photoinduced charge transfer and separation events in a newly synthesized azobenzene-bridged perylenediimide-dimer (PDI-dimer) are demonstrated. Trans-to-cis conversion (∼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.
Palabras clave/Materias:
azobenzene
excited state charge transfer
perylenediimide dimer
symmetry breaking
trans-cis isomerization
Tipo documento :
application/pdf
Derechos de acceso:
info:eu-repo/semantics/openAccess
DOI :
https://doi.org/10.1002/chem.202102903
Aparece en las colecciones:
Artículos Farmacología, Pediatría y Química Orgánica



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