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modifications have been carried out in recent years affecting each component of the complexes: terpyridines have been replaced by quaterpyridines; other metals were used instead of ruthenium, and thiocyanates have been replaced by different pinchers in order to achieve cyclometalated or heteroleptic complexes.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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http://dx.doi.org/10.3390/ma9030137 | DOI Listing |
Materials (Basel)
February 2016
Department of Chemistry and NIS Interdepartmental Centre, University of Torino, Via Giuria 7, I-10125 Torino, Italy.
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.
View Article and Find Full Text PDFBeilstein J Org Chem
December 2015
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse, France ; Université de Toulouse, UPS, INP, LCC, F-31077 Toulouse, France.
Quaterpyridines have been demonstrated to be useful building blocks in metallo-supramolecular chemistry; however, their synthesis requires the preparation of sensitive building blocks. We present here three examples of nonsymmetric quaterpyridines that were easily obtained in yields of 70-85% by condensation of commercially available enones with 6-acetyl-2,2':6',2''-terpyridine through a Kröhnke pyridine synthesis. Easy access to 6-acetyl-2,2':6',2''-terpyridine starting from 2,6-diacetylpyridine and 2-acetylpyridine is described.
View Article and Find Full Text PDFInorg Chem
December 2015
Advanced Materials Engineering and Modelling Group, Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
Acta Crystallogr E Crystallogr Commun
September 2015
Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
We report the structural characterization of [6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine](2,2'-bi-pyridine)-chlorido-ruthenium(II) hexa-fluorido-phosphate, [RuCl(C10H8N2)(C30H20N6)]PF6, which contains the bidentate ligand 2,2'-bi-pyridine (bpy) and the tridendate ligand 6',6''-bis-(pyridin-2-yl)-2,2':4',4'':2'',2'''-quaterpyridine (tpy-tpy). The [RuCl(bpy)(tpy-tpy)](+) monocation has a distorted octa-hedral geometry at the central Ru(II) ion due to the restricted bite angle [159.32 (16)°] of the tridendate ligand.
View Article and Find Full Text PDFMolecules
August 2014
Department of Chemistry, University of Fort Hare, P.M.B. X1314, Alice 5700, South Africa.
A number of novel ruthenium(II) polypyridine complexes have been designed and synthesized for use as photosensitizers in dye-sensitized solar cells (DSSCs) due to their rich photophysical properties such as intense absorption, long-lived lifetimes, high emission quantum yields and unique redox characteristics. Many of these complexes exhibit photophysical behavior that can be readily controlled through a careful choice of ligands and/or substituents. With this perspective, we review the design and general synthetic methods of some polypyridine ligands based on bipyridine, phenanthroline, terpyridine and quaterpyridine with/without anchoring groups with a view to correlate functionality of ligand structures with the observed photophysical, electroredox and power conversion efficiency of some examples of Ru(II) polypyridyl complexes that have been reported andparticularly used in the DSSCs applications.
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