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

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.