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dc.contributor.authorM. Ishida-
dc.contributor.authorJ. L. Sessler-
dc.identifier.citationVOL 115, NO 39, 19343-19354-
dc.description.abstractNovel zinc porphyrin dyes for use in dyesensitized solar cells (DSSCs) have been synthesized. These dyes are based on a molecular design that relies on donor-π-acceptor interactions, a concept implemented by introducing a bis(4-tert-butylphenyl)amino group at the meso position of the porphyrin opposite to what are 2-propenoic or 2,4- pentadienoic acid anchoring groups at the β-pyrrolic positions. Incorporating an electron-donating group (i.e., the diarylamine) on the porphyrin core serves as the considerable electronic coupling between the donor site and porphyrin core, and hence, the HOMO-LUMO energy gap is decreased. This change is reflected in the remarkable red shift and broadening of the absorption spectra relative to an unfunctionalized parent system. This substitution, in conjunction with functionalization with carboxylic acid moieties on the β-pyrrolic positions, also provides what is an effectively aligned donor-π-acceptor dipolar architecture. This, in turn, gives rise to advantageous chargetransfer properties, including what are significant improvements of the electron injection efficiency on titanium oxide (TiO2) compared to our previous models without a donor substituent. The DSSCs of this study were composed of zero-dimensional hierarchical structured TiO2 spheres with a diameter of 600-800 nm prepared from P-25 and anatase TiO2 nanoparticles, which functioned as the photoelectrodes. With the anatase TiO2-based DSSCs, the power conversion efficiencies (η) as well as the photocurrent action spectra were relatively enhanced, an effect ascribed to the characteristic mesoporous effect and associated electrophysical properties of the anatase TiO2 spheres. Among the dyes prepared in the context of the present study, the doubly functionalized carboxylic acid derivative, tda-2b-bd-Zn, gave rise to the highest power conversion. The η value was 7.47%, and the maximum incident photon-to-c-
dc.publisherThe journal of physical chemistry. C, Nanomaterials and Interfaces-
dc.subjectdye-sensitized solar cell-
dc.subjectporphyrin dyes-
dc.subjectMesoporous TiO2 Spheres-
dc.titleDonor-Substituted β-Functionalized Porphyrin Dyes on Hierarchically Structured Mesoporous TiO2 Spheres. Highly Efficient Dye-Sensitized Solar Cells-
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