1. Synthesis and properties of [Pt(4-CO(2)CH(3)-py)(2)(mnt)]: comparison of pyridyl and bipyridyl-based dyes for solar cells.
- Author
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Moorcraft LP, Morandeira A, Durrant JR, Jennings JR, Peter LM, Parsons S, Turner A, Yellowlees LJ, and Robertson N
- Subjects
- Coloring Agents chemistry, Electrochemistry, Electron Spin Resonance Spectroscopy, Electron Transport, Kinetics, Organometallic Compounds chemistry, Quantum Theory, Spectrophotometry, Ultraviolet, 2,2'-Dipyridyl chemistry, Coloring Agents chemical synthesis, Organometallic Compounds chemical synthesis, Platinum chemistry, Solar Energy
- Abstract
The dye complexes [Pt(4-CO(2)R-py)(2)(mnt)] (R = H (3a), CH(3) (3b)) and the precursor complexes [Pt(4-CO(2)R-py)(2)Cl(2)] (2a, 2b) (py = pyridyl) were synthesised, characterised by electrochemical, spectroscopic, spectroelectrochemical (UV-vis-nIR and in situ EPR) and hybrid DFT computational methods and attached to a TiO(2) substrate to determine charge recombination kinetics. The results were compared to the bipyridyl analogues [Pt{X,X'-(CO(2)R)-2,2'-bipyridyl}(mnt)], (X = 3 or 4). The electronic characteristics of the bis-pyridyl complex were found to be different to the bipyridyl complexes making the former harder to reduce, shifting the lowest-energy absorption band to higher energy and showing separate degenerate LUMO orbitals on the two pyridine rings. The latter point determines that the di-reduced pyridyl complex remains EPR active, unlike the bipyridyl analogue. Complex 3a attached to nanocrystalline TiO(2) shows a long charge recombination lifetime in comparison with the analogous complex with the ubiquitous 4,4'-(CO(2)H)(2)-bipyridyl ligand, suggesting that pyridyl complexes may possess some advantage over bipyridyl complexes in dye-sensitised solar cells.
- Published
- 2008
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