Synthesis and Photovoltaic Properties of Phenylethynyl-substituted Diazaporphyrin

Kurotobi, Kei; Kawamoto, Kyosuke; Toude, Yuuki; Fujimori, Yamato; Kinjo, Yuriko; Ito, Seigo; Matano, Yoshihiro; Imahori, Hiroshi

doi:10.1246/cl.130212

Cited by 10 publications

(9 citation statements)

References 17 publications

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“…Dye-sensitized solar cells (DSSCs) have attracted much attention due to their excellent photovoltaic performance, low production costs, and environmentally friendly features. − The original form of DSSCs has been realized in the ruthenium(II) bipyridyl complexes where a solar-to-electric power conversion (PCE) of about 12% has been reported. , Despite a high PCE and tunability of electronic properties, their extensive application has been limited because of the rarity, requirement for careful synthesis, and environmental issues associated with ruthenium metal. , From this perspective, organic dyes with no metal or inexpensive metal complexes have become the central focus of DSSCs due to low-cost production and facile modulation of their electronic structure to improve their light-harvesting efficiency . An elegant strategy to improve the light-harvesting ability of the sensitizers is to use an electron donor (D, push) and electron acceptor (A, pull) group, connected via a π-conjugated bridge. , Separating donor from acceptor in the so-called donor−π–acceptor or push–pull dyes allows the spatial separation of electrons and holes and thus decreases their recombination rate (i.e., increasing exciton lifetimes).…”

Section: Introductionmentioning

confidence: 99%

Designing Push–Pull Porphyrins for Efficient Dye-Sensitized Solar Cells

Parsa

Safari

2018

J. Phys. Chem. A

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Over the past decade, tremendous effort has been made to improve the light-harvesting ability of push-pull porphyrin dyes. Despite notable success achieved in this direction, push-pull porphyrin dyes still suffer from a poor light-harvesting efficiency owing to the lack of absorption between the Soret and Q-bands. To tackle this issue, here we design a series of push-pull porphyrin dyes with anchoring groups either at meso- or β-position using calculations based on first-principles time-dependent density functional theory. In contrast to the common perception, we find that porphyrin dyes bearing an electron-donor at the meso-position and an electron-acceptor at the β-position produce an additional extended band between the Soret and Q-bands appearing at around 500 nm due to S → S excitation, leading to a much higher light-harvesting performances compared to meso- and β-disubstituted ones. In addition, changing the π-conjugated linker at the acceptor site from ethylene linker (C═C) to acetylene linker (C≡C) further improves the light-harvesting ability of meso-β-porphyrin dyes, making them promising candidates for dye-sensitized solar cell application.

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Section: Introductionmentioning

confidence: 99%

Designing Push–Pull Porphyrins for Efficient Dye-Sensitized Solar Cells

Parsa

Safari

2018

J. Phys. Chem. A

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“… a λ max (log ε), absorption maxima (logarithms of extinction coefficients). For details, see refs , , , , , , , , , , , and . …”

Section: Azaporphyrins and Related Compoundsmentioning

confidence: 99%

“…The treatment of Br-MDAPs 72M (M = Zn, Ni) with tris(isopropyl)silylacetylene under standard Sonogashira reaction conditions, followed by the deprotection of the silyl group in the coupling products, afforded the corresponding 3-ethynyl-MDAPs 76M in 87−91% yields (Scheme 39). 148,149 Furthermore, ethynyl-ZnDAP 76Zn underwent a second Sonogashira reaction with ethyl p-iodobenzoate to give 3-(4carboxypheny)ethynyl-ZnDAP 77 in 24% yield after alkaline hydrolysis. 148 Shinokubo et al reported the direct and regioselective functionalization of NiDAP 66Ni with organometallic reagents.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Synthesis of Aza-, Oxa-, and Thiaporphyrins and Related Compounds

Matano

2016

Chem. Rev.

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113

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Chemical modification at the periphery with nitrogen or chalcogens is a highly promising strategy to diversify the optical, electrochemical, magnetic, and coordination properties of the porphyrin family. Indeed, various kinds of phthalocyanines and related benzo-annelated azaporphyrinoids have been synthesized, and their fundamental properties have been extensively investigated. However, the synthesis of heteroatom-containing porphyrins in which the peripheral methine groups are partially replaced with nitrogen or chalcogens remains a considerable challenge. In this review, we will focus mainly on recent advances in the synthesis of aza-, oxa-, and thiaorphyrins and related compounds, including historically important examples.

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“…In 2013, we reported the first example of a DAP‐based DSSC, in which P4 was used as a sensitizer (Figure ) . Unfortunately, the PCE of this P4 ‐based DSSC was very low (0.08 %), not only because of the small driving force for electron injection from the excited state of P4 to the CB of TiO 2 , but also owing to the insufficient light‐harvesting ability in the long‐wavelength visible region.…”

Section: Introductionmentioning

confidence: 99%

Unsymmetrically Substituted Donor–π–Acceptor‐Type 5,15‐Diazaporphyrin Sensitizers: Synthesis, Optical and Photovoltaic Properties

et al. 2017

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IntroductionDonor-p-acceptor( D-p-A)-type porphyrin derivatives have attracted considerable attention as functional dyes in the fields of dye-sensitized solar cells (DSSCs) and nonlinearo ptics (NLO) because they have intrinsically narrow HOMO-LUMO gaps and polarized excited states with al arge charge-transfer (CT) character. [1][2][3] For example, DSSCs composed of TiO 2 and aD -p-Atype porphyrin, such as SM315, [1f] exhibit high powerc onversion efficiencies (PCEs), whereas acetylene-linked D-p-A-type porphyrins, such as P1, [3a] show strongs econd-order NLO activity and have been used as dyes for second-harmonic generation imaging (Figure 1). In DSSCs, the D-p-A structure is indis-pensablef or acceleration of chargei njection from the excited state of the dye to the conduction band (CB) of TiO 2 ,a sw ell asThe first examples of unsymmetrical b-substituted donor-p-acceptor (D-p-A)-type 5,15-diazaporphyrin (DAP) sensitizers with both p-aminophenyl and p-carboxyphenyl groups at their peripheral 3-, 7-, 13-, and/or1 7-positions have been synthesized for use in dye-sensitized solar cells (DSSCs). UV/Vis absorption and emission spectroscopy,e lectrochemical measurements, and DFT calculations revealed that these D-p-A dyes exhibit high light-harvestingp roperties overt he whole visible range because of the intrinsic charge-transferc haracter of their elec-tronic transitions. The cell performances of TiO 2 -based DSSCs fabricated with the newly prepared DAP derivatives were evaluated under standard AM1.5 conditions. Among the four dyes examined, 13,17-bis(p-carboxyphenyl)-3,7-bis[p-(N,N-dimethylamino)phenyl]-DAP showedt he highest powerc onversion efficiency( 2.0 %), which was 20 times larger than that obtained with 3-(p-carboxyphenyl)-DAP. These results show that the DAP chromophore could be used as the electron-accepting p unit in varioustypes of functional dyes.[a] Prof.

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Synthesis and Photovoltaic Properties of Phenylethynyl-substituted Diazaporphyrin

Cited by 10 publications

References 17 publications

Designing Push–Pull Porphyrins for Efficient Dye-Sensitized Solar Cells

Designing Push–Pull Porphyrins for Efficient Dye-Sensitized Solar Cells

Synthesis of Aza-, Oxa-, and Thiaporphyrins and Related Compounds

Unsymmetrically Substituted Donor–π–Acceptor‐Type 5,15‐Diazaporphyrin Sensitizers: Synthesis, Optical and Photovoltaic Properties

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