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A multitechnique physicochemical investigation of various factors controlling the photoaction spectra and of some aspects of the electron transfer for a series of push-pull Zn(II) porphyrins acting as dyes in DSSCs (Articolo in rivista)

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A multitechnique physicochemical investigation of various factors controlling the photoaction spectra and of some aspects of the electron transfer for a series of push-pull Zn(II) porphyrins acting as dyes in DSSCs (Articolo in rivista) (literal)

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Orbelli Biroli, A.; Tessore, F.; Pizzotti, M.; Biaggi, C.; Ugo, R.; Caramori, S.; Aliprandi, A.; Bignozzi, C. A.; De Angelis, F.; Giorgi, G.; Licandro, E.; Longhi, E. (2011)
A multitechnique physicochemical investigation of various factors controlling the photoaction spectra and of some aspects of the electron transfer for a series of push-pull Zn(II) porphyrins acting as dyes in DSSCs
in Journal of physical chemistry. C; AMER CHEMICAL SOC, 1155 16TH ST, NW, WASHINGTON, DC 20036 (Stati Uniti d'America)
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Orbelli Biroli, A.; Tessore, F.; Pizzotti, M.; Biaggi, C.; Ugo, R.; Caramori, S.; Aliprandi, A.; Bignozzi, C. A.; De Angelis, F.; Giorgi, G.; Licandro, E.; Longhi, E. (literal)

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CNR-ISTM, via C. Golgi 19, 20133 Milano, Italy Dip. CHimica Inorganica Metallorganica e Analitica \"Lamberto Malatesta\", Università degli Studi di Milano, via G. Venezian 21, 20133 Milano, Italy Dip. Chimica, Università degli Studi di Ferrara, via L. Borsari 46, 44121 Ferrara, Italy CNR-ISTM, c/o Dip. Chimica, Università degli Studi di Perugia, via Elce di SOtto 8, 06123 Perugia, Italy Dip. Chimica Organica e Industriale, via C. Golgi 19, 20133 Milano, Italy (literal)

Titolo

A multitechnique physicochemical investigation of various factors controlling the photoaction spectra and of some aspects of the electron transfer for a series of push-pull Zn(II) porphyrins acting as dyes in DSSCs (literal)

Abstract

A multitechnique physicochemical comparative investigation involving TDDFT theoretical calculations, steadystate and time-resolved electronic absorption spectra, and electrochemical and photoelectrochemical investigations was carried out on a family of push-pull porphyrinic sensitizers ([5-(4'-carboxyphenylethynyl)-15-(4\"-methoxy-phenylethynyl)-10,20-bis(3,5-ditert-butylphenyl)porphyrinate]Zn(II) (1) and [5-(4'-carboxy-phenylethynyl)-15-(4\"-N,N-dimethylamino-phenylethynyl)-10,20-bis-(3,5-di-tert-butylphenyl)porphyrinate]Zn(II) (2) and the new fluorinated porphyrinic dye [5-(4'-carboxy-20,30,50,60-tetrafluorophenylethynyl)-15-(4\"-N,N-dimethylamino-phenylethynyl)-10,20-bis(3,5-di-tert-butylphenyl)porphyrinate]Zn(II) (3)) with the aim of identifying the structurally related electronic properties at the basis of efficient interfacial charge separation. We found for all dyes a photoconversion nearly twice more effective for the B band than for the Q band, which could not be explained only by considerations based on the electron collection efficiency but also by a more energetically favorable electron injection from the S2 excited state. The lower photoconversion of the fluorinated dye 3, when compared to dyes 1 and 2, was explained not only by a more difficult absorption on the TiO2 photoanode but also by a lower electron injection efficiency and a less successful hole transfer to the electrolyte, leading to increased charge recombination. (literal)

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