Ruthenium(II) Sensitizers with Heteroleptic Tridentate Chelates for Dye‐Sensitized Solar Cells

Chou, Chien-Chang; Wu, Kuan‐Lin; Chi, Yun; Hu, Wei–Ping; Yu, Shuchun Joyce; Lee, Gene‐Hsiang; Lin, Chia-Feng; Chou, Pi‐Tai

doi:10.1002/anie.201006629

Cited by 203 publications

(110 citation statements)

References 54 publications

(18 reference statements)

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“…These dyes overcome the efficiency of BD tested in the same conditions ( η = 10.05 vs 9.07% ; TiO 2 : 18 + 4 μm, dye: 0.3 mM DMF / t -butanol 1:1 with 10 mM DCA, electrolyte: 0.6 M DMPII, 0.1 M I 2 , 0.1 M LiI, 0.5 M t-bupy in CH 3 CN) due to their higher molar extinction coefficients between 400 and 550 nm and their extended absorption up to 850 nm, as a consequence of the HOMO destabilization by the pyrazole. The same group reported, in 2011 [128], a series of tridentate 2,6-bis(3-pyrazolyl)pyridine ligands bearing various substitutions in 4- position ( 33 , Figure 26). The reported IPCE spectra showed a worse sensitization in the NIR region with respect to N749 but a better conversion in the visible range which accounts for efficiencies up to 10.7% (TiO 2 : 15 + 5 μm, dye: 0.3 mM ethanol / DMSO 4:1 with 1M CDCA, electrolyte: 0.6 M DMPII, 0.1 M I 2 , 0.5 M t-bupy, 0.1 M LiI in CH 3 CN).…”

Section: Modifications Of Black Dye and Structure-properties Relatmentioning

confidence: 99%

Terpyridine and Quaterpyridine Complexes as Sensitizers for Photovoltaic Applications

et al. 2016

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Terpyridine and quaterpyridine-based complexes allow wide light harvesting of the solar spectrum. Terpyridines, with respect to bipyridines, allow for achieving metal-complexes with lower band gaps in the metal-to-ligand transition (MLCT), thus providing a better absorption at lower energy wavelengths resulting in an enhancement of the solar light-harvesting ability. Despite the wider absorption of the first tricarboxylate terpyridyl ligand-based complex, Black Dye (BD), dye-sensitized solar cell (DSC) performances are lower if compared with N719 or other optimized bipyridine-based complexes. To further improve BD performances several modifications have been carried out in recent years affecting each component of the complexes: terpyridines have been replaced by quaterpyridines; other metals were used instead of ruthenium, and thiocyanates have been replaced by different pinchers in order to achieve cyclometalated or heteroleptic complexes. The review provides a summary on design strategies, main synthetic routes, optical and photovoltaic properties of terpyridine and quaterpyridine ligands applied to photovoltaic, and focuses on n-type DSCs.

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Section: Modifications Of Black Dye and Structure-properties Relatmentioning

confidence: 99%

Terpyridine and Quaterpyridine Complexes as Sensitizers for Photovoltaic Applications

et al. 2016

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“…34 Finally, a 1-bpp/fluorene copolymer that was assembled through multiple Sonogashira couplings 55 ( The most success has been achieved with complexes related to I, bearing thienyl substituents at either the 3-bpp ligand (R 1 ) or the terpy derivative (R 2 ). 53,121 Conjugation of the acceptor ligand to the thienyl group red-shifts the complexes' absorption across the full visible spectrum. Using I, DSCs with photoconversion 85 efficiencies of up to 10.7 % have been prepared, comparable to those using [Ru(NCS) 3 performance to an analogue with the carboxy groups on the bipy co-ligand.…”

Section: F-block Complexesmentioning

confidence: 99%

Recent advances in the synthesis and applications of 2,6-dipyrazolylpyridine derivatives and their complexes

Halcrow

2014

New J. Chem.

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Developments in the chemistry of 2,6-di(pyrazol-1-yl)pyridine (1-bpp) and 2,6-di(pyrazol-3-yl)pyridine (3-bpp), their derivatives and their complexes are surveyed, with emphasis on the last eight years. Particular advances include the synthesis of multi-functional spin-crossover switches; the incorporation of emissive f-element podand centres into biomedical sensors; the self-assembly of a variety of functional soft materials and surface structures; and, the use of 3-bpp complexes in catalysis.

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“…12d). 16 These pyrazolyl ligands have again been substituted with strongly electron-withdrawing -CF 3 groups to tune the electron-donating character of the dianionic ligands in order to maintain a sufficient driving force for dye regeneration by the electrolyte (the Ru(III)/ Ru(II) redox couple lies at +0.95 V vs. NHE). A key advantage of this molecular framework is that it is completely devoid of the labile NCS − ligand and that it is readily modifiable at the 4′-position of the central pyridyl ring.…”

Section: Black Dye Analoguesmentioning

confidence: 99%

Cycloruthenated sensitizers: improving the dye-sensitized solar cell with classical inorganic chemistry principles

2012

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A divergence from the conventional approach to chromophore design has led to the establishment of many exciting new benchmarks for the dye-sensitized solar cell (DSSC), including the first documented power conversion efficiency in excess of 12% at 1 sun illumination [Yella et al., Science 2011, 334, 629]. Paramount to these advances is the deviation from polypyridyl ruthenium dyes bearing NCS(-) ligands, such as [Ru(dcbpy)(2)(NCS)(2)] (N3; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine). While metal-free and porphyrin dyes have demonstrated much promise, the discovery that the NCS(-) ligands of N3 can be replaced by anionic, chelating cyclometalating ligands without compromising device efficiencies has ushered in a new era of ruthenium dye development. A particularly appealing feature of this class of dyestuff is that they offer acute control of the frontier molecular orbitals to enable the precise attenuation of both the ground and excited state redox potentials through judicious chemical modification of the aryl ring. This Perspective summarizes very recent developments in the field, and demonstrates how the new and rapidly expanding class of Ru-based sensitizers provides a conduit for enhancing the performance (and potentially the stability) of the DSSC.

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Ruthenium(II) Sensitizers with Heteroleptic Tridentate Chelates for Dye‐Sensitized Solar Cells

Cited by 203 publications

References 54 publications

Terpyridine and Quaterpyridine Complexes as Sensitizers for Photovoltaic Applications

Terpyridine and Quaterpyridine Complexes as Sensitizers for Photovoltaic Applications

Recent advances in the synthesis and applications of 2,6-dipyrazolylpyridine derivatives and their complexes

Cycloruthenated sensitizers: improving the dye-sensitized solar cell with classical inorganic chemistry principles

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