Porphyrins with β-acetylene-bridged functional groups for efficient dye-sensitized solar cells

Sakurada, Tomoaki; Arai, Yonbon; Segawa, Hiroshi

doi:10.1039/c3ra41317a

Cited by 25 publications

(6 citation statements)

References 45 publications

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“…The authors suggested that the superior electron- withdrawing ability of cyano group first pull the electrons and then transfer them back into the porphyrin core. Another case is the ZnPF and ZnPH porphyrins (shown in Figure S4 ), which were reported by Imahori et al in 2011 (Mathew et al, 2011 ; Sakurada et al, 2014 ). ZnPF featured with 4 fluorine atoms substituted on the phenyl linker, supposed to enhance the electron-withdrawing ability of the acceptor.…”

Section: The Development Of Porphyrins For Solar Cell Applicationsupporting

confidence: 58%

Push-Pull Zinc Porphyrins as Light-Harvesters for Efficient Dye-Sensitized Solar Cells

Liu

Wang

2018

Front. Chem.

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Dye-sensitized solar cell (DSSC) has been attractive to scientific community due to its eco-friendliness, ease of fabrication, and vivid colorful property etc. Among various kinds of sensitizers, such as metal-free organic molecules, metal-complex, natural dyes etc., porphyrin is one of the most promising sensitizers for DSSC. The first application of porphyrin for sensitization of nanocrystaline TiO2 can be traced back to 1993 by using [tetrakis(4-carboxyphenyl) porphyrinato] zinc(II) with an overall conversion efficiency of 2.6%. After 10 years efforts, Officer and Grätzel improved this value to 7.1%. Later in 2009, by constructing porphyrin sensitizer with an arylamine as donor and a benzoic acid as acceptor, Diau and Yeh demonstrated that this donor-acceptor framwork porphyrins could attain remarkable photovoltaic performance. Now the highest efficiencies of DSSC are dominated by donor-acceptor porphyrins, reaching remarkable values around 13.0% with cobalt-based electrolytes. This achievement is largely contributed by the structural development of donor and acceptor groups within push-pull framwork. In this review, we summarized and discussed the developement of donor-acceptor porphyrin sensitizers and their applications in DSSC. A dicussion of the correlation between molecular structure and the spectral and photovoltaic properties is the major target of this review. Deeply dicussion of the substitution group, especially on porphyrin's meso-position were presented. Furthermore, the limitations of DSSC for commercialization, such as the long-term stability, sophisticated synthesis procedures for high efficiency dye etc., have also been discussed.

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Section: The Development Of Porphyrins For Solar Cell Applicationsupporting

confidence: 58%

Push-Pull Zinc Porphyrins as Light-Harvesters for Efficient Dye-Sensitized Solar Cells

Liu

Wang

2018

Front. Chem.

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“…β‐Substitution is known to cause a redshift of the B band, and a smaller redshift of the Q bands 2. 11, 21–24 A study in which the substituent and the substitution position ( meso or β) is varied suggests that the redshift in absorption is influenced more by the substituent extending conjugation (ethynyl linker caused further redshifting) while the broadening of the B band was influenced more by the position (β broader than meso ) 25. Here the position of the B band shows some variation with R′/R′′, and this also has some effect on the band broadness, as all are substituted at the β‐position.…”

Section: Resultsmentioning

confidence: 99%

Flexible Tuning of Unsaturated β‐Substituents on Zn Porphyrins: A Synthetic, Spectroscopic and Computational Study

Salm

Wagner

et al. 2015

Chemistry A European J

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A series of zinc porphyrins substituted at adjacent β-positions with a CN group and para-substituted ethenyl/ethynyl-phenyl group have been studied using electronic absorption spectroscopy, resonance Raman spectroscopy and DFT calculations. The oxidative nucleophilic substitution of hydrogen was utilized for the introduction of a cyano substituent on the porphyrin ring. This modification has a remarkable electronic effect on the ring. The resulting porphyrin cyanoaldehyde was further modified in Wittig condensations to give series of arylalkene- and arylalkyne-substituted derivatives. This substitution pattern caused significant redshifting and broadening of the B band, tuning from 433-446 nm. Additionally the Q/B band intensity ratios show much higher values than observed for the parent porphyrin ZnTPP (0.20 vs. 0.03). Careful analysis of the electronic transitions using DFT and resonance Raman spectroscopy reveal that the substituent does not significantly perturb the electronic structure of the porphyrin core, which is still well described by Gouterman's four-orbital model. However, the substituents do play a role in elongating the conjugation length and this results in the observed spectral changes.

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“…As discussed later in detail in Section 4, DFT calculations have shown that, comparing with the reference unsubstituted Zn II tetraarylporphyrin (ZnTPP), the presence of electron withdrawing groups on the  substituent modulates the absorption spectrum stabilizing the energies of the LUMO and LUMO+2 orbitals, with an extension of these orbitals onto the  substituent which implies an increased tendency of electron transfer from the porphyrinic core to the  substituent and consequently to the TiO2 surface [66]. Later Arai, Segawa et al [67] reported a series of tetraphenyl Zn II porphyrins with one or two acetylenic functional groups at the  pyrrolic position (Figure 5). The green doubly substituted Zn II porphyrin 11 leads, in the presence of coadsorbate chenodeoxycholic acid (CDCA) to a near unity IPCE value, surpassing IPCE maxima of the purple mono substituted derivative.…”

Section: Tetraaryl Substituted Zn II Porphyrinsmentioning

confidence: 99%

“…The first attempt to gain structure/activity relationships involving charge transfer dynamics from a series of natural β-substituted chlorophyll derivatives, and their slightly modified synthetic derivatives (Figure 25) dates back to 1993 [64]. Chlorophylla (67) does not adsorb efficiently on TiO2 from most of polar organic solvents, due to the weak interaction of the ester and keto carbonyl groups with the oxide surface. However adsorption takes place quite efficiently (A670 = 0.3) from diethyl ether or hexane solutions.…”

Section: Electron Transfer Kineticsmentioning

confidence: 99%

β-Substituted ZnII porphyrins as dyes for DSSC: A possible approach to photovoltaic windows

Carlo

Biroli

Tessore

et al. 2018

Coordination Chemistry Reviews

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Porphyrins with β-acetylene-bridged functional groups for efficient dye-sensitized solar cells

Cited by 25 publications

References 45 publications

Push-Pull Zinc Porphyrins as Light-Harvesters for Efficient Dye-Sensitized Solar Cells

Push-Pull Zinc Porphyrins as Light-Harvesters for Efficient Dye-Sensitized Solar Cells

Flexible Tuning of Unsaturated β‐Substituents on Zn Porphyrins: A Synthetic, Spectroscopic and Computational Study

β-Substituted ZnII porphyrins as dyes for DSSC: A possible approach to photovoltaic windows

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