Tetraaryl ZnII Porphyrinates Substituted at -Pyrrolic Positions as Sensitizers in Dye-Sensitized Solar Cells: A Comparison with meso-Disubstituted Push-Pull ZnII Porphyrinates

被引：57

作者：

Di Carlo, Gabriele ^{[1
]}

Biroli, Alessio Orbelli ^{[2
]}

Pizzotti, Maddalena ^{[1
]}

Tessore, Francesca ^{[1
]}

Trifiletti, Vanira ^{[3
,4
]}

Ruffo, Riccardo ^{[3
,4
]}

Abbotto, Alessandro ^{[3
,4
]}

Amat, Anna ^{[5
]}

De Angelis, Filippo ^{[5
]}

Mussini, Patrizia R. ^{[1
]}

机构：

[1] Univ Milan, INSTM, Unita Ric, Dipartimento Chim, I-20133 Milan, Italy

[2] CNR, ISTM, I-20133 Milan, Italy

[3] Univ Milano Bicocca, Solar Energy Res Ctr MIB SOLAR, Dept Mat Sci, I-20125 Milan, Italy

[4] Univ Milano Bicocca, INSTM Res Unit, I-20125 Milan, Italy

[5] CNR, ISTM, Computat Lab Hybrid Organ Photovolta CLHYO, I-06123 Perugia, Italy

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 32期

关键词：

cyclic voltammetry; density functional calculations; porphyrins; push-pull systems; solar cells; ELECTRONIC CHARACTERIZATION; ZINC PORPHYRIN; ORGANIC-DYES; TIO2; LIGHT; SPECTRA; COADSORBENT; DERIVATIVES; POTENTIALS; MODULATION;

D O I：

10.1002/chem.201300219

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A facile and fast approach, based on microwave-enhanced Sonogashira coupling, has been employed to obtain in good yields both mono-and, for the first time, disubstituted pushpull ZnII porphyrinates bearing a variety of ethynylphenyl moieties at the bpyrrolic position(s). Furthermore, a comparative experimental, electrochemical, and theoretical investigation has been carried out on these b-monoor disubstituted ZnII porphyrinates and meso-disubstituted push-pull ZnII porphyrinates. We have obtained evidence that, although the HOMO-LUMO energy gap of the meso-substituted push-pull dyes is lower, so that charge transfer along the push-pull system therein is easier, the b-mono-or disubstituted push-pull porphyrinic dyes show comparable or better efficiencies when acting as sensitizers in DSSCs. This behavior is apparently not attributable to more intense B and Q bands, but rather to more facile charge injection. This is suggested by the DFT electron distribution in a model of a bmonosubstituted porphyrinic dye interacting with a TiO2 surface and by the positive effect of the b substitution on the incident photon-to-current conversion efficiency (IPCE) spectra, which show a significant intensity over a broad wavelength range (350-650 nm). In contrast, meso-substitution produces IPCE spectra with two less intense and well-separated peaks. The positive effect exerted by a cyanoacrylic acid group attached to the ethynylphenyl substituent has been analyzed by a photophysical and theoretical approach. This provided supporting evidence of a contribution from chargetransfer transitions to both the B and Q bands, thus producing, through conjugation, excited electrons close to the carboxylic anchoring group. Finally, the straightforward and effective synthetic procedures developed, as well as the efficiencies observed by photoelectrochemical measurements, make the described b-monosubstituted ZnII porphyrinates extremely promising sensitizers for use in DSSCs.

引用

页码：10723 / 10740

页数：18

共 61 条

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