Excited State Charge Separation in an Azobenzene‐Bridged Perylenediimide Dimer – Effect of Photochemical Trans‐Cis Isomerization
| العنوان: | Excited State Charge Separation in an Azobenzene‐Bridged Perylenediimide Dimer – Effect of Photochemical Trans‐Cis Isomerization |
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| المؤلفون: | Fernando Fernández-Lázaro, Francis D'Souza, David Gutiérrez-Moreno, Sairaman Seetharaman, Nathalie Zink-Lorre, Paul A. Karr |
| المصدر: | Chemistry (Weinheim an Der Bergstrasse, Germany) |
| بيانات النشر: | Wiley, 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | inorganic chemicals, Quenching (fluorescence), Full Paper, Chemistry, perylenediimide dimer, Dimer, Organic Chemistry, Charge (physics), General Chemistry, Full Papers, Photochemistry, symmetry breaking, Catalysis, nervous system diseases, body regions, chemistry.chemical_compound, azobenzene, Azobenzene, Excited state, Ultrafast laser spectroscopy, trans-cis isomerization, Isomerization, excited state charge transfer, Cis–trans isomerism |
| الوصف: | 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. Excited state charge transfer and charge separation events in a newly synthesized azobenzene bridged PDI‐dimer are demonstrated. Photoconversion of trans to cis‐isomer accelerated the photoevents to an appreciable level. |
| تدمد: | 1521-3765 0947-6539 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::17e12ba65224b78a606cfd3273dda6ff https://doi.org/10.1002/chem.202102903 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....17e12ba65224b78a606cfd3273dda6ff |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15213765 09476539 |
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