Synthesis and properties of [Pt(4-CO2CH3-py)2(mnt)]: Comparison of pyridyl and bipyridyl-based dyes for solar cells

Lucy P. Moorcraft, Ana Morandeira, James R. Durrant, James R. Jennings, Laurence M. Peter, Simon Parsons, Andrew Turner, Lesley J. Yellowlees, Neil Robertson

Research output: Contribution to journalArticlepeer-review

Abstract

The dye complexes [Pt(4-CO2R-py)2(mnt)] (R = H (3a), CH3 (3b)) and the precursor complexes [Pt(4-CO2R-py)2Cl2] (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 TiO2 substrate to determine charge recombination kinetics. The results were compared to the bipyridyl analogues [Pt{X, X'-(CO2R)-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 TiO2 shows a long charge recombination lifetime in comparison with the analogous complex with the ubiquitous 4,4'-(CO2H)2-bipyridyl ligand, suggesting that pyridyl complexes may possess some advantage over bipyridyl complexes in dye-sensitised solar cells.

Original languageEnglish
Pages (from-to)6940-6947
Number of pages8
JournalDalton Transactions
Issue number48
DOIs
Publication statusPublished - 28 Dec 2008

Keywords

  • DIIMINE-DITHIOLATE COMPLEXES
  • INTERFACIAL ELECTRON-TRANSFER
  • SQUARE-PLANAR
  • NANOCRYSTALLINE TIO2
  • EXCITED-STATES
  • METAL
  • DFT
  • COMPOUND
  • SERIES
  • TDDFT

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