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Directly Linked Zinc Phthalocyanine–Perylenediimide Dyads and a Triad for Ultrafast Charge Separation


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Title:
Directly Linked Zinc Phthalocyanine–Perylenediimide Dyads and a Triad for Ultrafast Charge Separation
Authors:
Zink Lorre, Nathalie
Font-Sanchis, Enrique  
Seetharaman, Sairaman
Karr, Paul A.
Sastre-Santos, Ángela
D’Souza, Francis
Fernández Lázaro, Fernando
Editor:
Wiley
Department:
Departamentos de la UMH::Farmacología, Pediatría y Química Orgánica
Issue Date:
2019
URI:
https://hdl.handle.net/11000/31047
Abstract:
Directly linked to promote strong intramolecular interactions, donor-acceptor dyads and a donor-acceptor-donor triad featuring zinc phthalocyanine (ZnPc) as electron donor and perylenediimide (PDI) as electron acceptor have been synthesized and characterized. Owing to complementary absorption features of the entities, improved light absorption was witnessed in these conjugates. The optimized geometry and electronic structures showed the majority of the highest occupied molecular orbital (HOMO) on the ZnPc entity, whereas the lowest unoccupied molecular orbital (LUMO) was on the PDI entity, suggesting that the charge-separated states would be ZnPc+ -PDI. - . The electrochemical and free-energy calculations suggested exothermic energy and/or electron transfer processes via the singlet states of PDI or ZnPc entities depending on the excitation wavelength of the laser used. The measured rates using femtosecond pump-probe spectroscopy coupled with global analysis of transient data revealed ultrafast energy transfer from 1 PDI* to ZnPc followed by charge separation. However, when ZnPc was selectively excited, only electron transfer was witnessed wherein the time constants for forward and reverse electron transfer processes followed Marcus predictions. The absorption in a wide section of the solar spectrum and the ultrafast charge separation suggest the usefulness of these systems as good photosynthetic models.
Keywords/Subjects:
charge separation
donor-acceptor conjugates
excitation transfer
perylenediimide
zinc phthalocyanine.
Type of document:
application/pdf
Access rights:
info:eu-repo/semantics/closedAccess
DOI:
https://doi.org/10.1002/chem.201900973
Appears in Collections:
Artículos Farmacología, Pediatría y Química Orgánica



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