Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells

K L McCall, James R Jennings, H X Wang, A Morandeira, Laurence M Peter, J R Durrant, L J Yellowlees, N Robertson

Research output: Contribution to journalArticle

  • 12 Citations

Abstract

We prepared the complexes [Ru{4,4′-(CO2R-bpy)2}{Cu(exoO2-cyclam)}][NO3]2 [R = Et (1), H (2)], which possess a CuII centre covalently linked to a (bipyridyl)RuII fragment. The complexes were characterised by cyclic voltammetry, UV/Vis spectroscopy, hybrid DFT and TD-DFT (time-dependent density-functional theory) calculations, EPR (electron paramagnetic resonance), emission spectroscopy and UV/Vis spectroelectrochemistry, with the latter showing reversible conversion to the mono- and di-oxidised and mono- and di-reduced species. The data suggest the first oxidation to be largely based on the Ru centre but with little energetic difference between the highest occupied orbitals based on Ru and based on Cu. There was also evidence of solvent coordination in both the electrochemistry and spectroelectrochemistry experiments. The redox potentials and the strongvisible absorptions of 2 (λmax = 562 nm, ϵmax = 22200 M–1 cm–1)make it appropriate for study as a sensitiser in a dye-sensitised solar cell. Charge-separated lifetime of photoexcited 2 on TiO2 and incident photon-to-current conversion efficiency (IPCE) as a function of wavelength were studied and are discussed alongside the formation of dye-sensitised solar cells with the best efficiency achieved of η = 2.55 %, Voc = 608 mV, Isc = 5.84 mA cm–2 and ff = 0.72. Limitations to the maximum efficiency obtained were attributed to a mismatch between the bipyridyl-based unoccupied orbital of the dye and the TiO2 conduction band edge.
LanguageEnglish
Pages589-596
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2011
Issue number4
DOIs
StatusPublished - Feb 2011

Fingerprint

Spectroelectrochemistry
2,2'-Dipyridyl
Emission spectroscopy
Electrochemistry
Conduction bands
Ultraviolet spectroscopy
Discrete Fourier transforms
Conversion efficiency
Cyclic voltammetry
Density functional theory
Paramagnetic resonance
Coloring Agents
Photons
Wavelength
Oxidation
Experiments
Dye-sensitized solar cells
cyclam
Oxidation-Reduction

Keywords

  • copper
  • dye-sensitized solar cells
  • dinuclear complexes
  • supramolecular chemistry
  • ruthenium

Cite this

Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells. / McCall, K L; Jennings, James R; Wang, H X; Morandeira, A; Peter, Laurence M; Durrant, J R; Yellowlees, L J; Robertson, N.

In: European Journal of Inorganic Chemistry, Vol. 2011, No. 4, 02.2011, p. 589-596.

Research output: Contribution to journalArticle

McCall, KL, Jennings, JR, Wang, HX, Morandeira, A, Peter, LM, Durrant, JR, Yellowlees, LJ & Robertson, N 2011, 'Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells' European Journal of Inorganic Chemistry, vol. 2011, no. 4, pp. 589-596. https://doi.org/10.1002/ejic.201001039
McCall, K L ; Jennings, James R ; Wang, H X ; Morandeira, A ; Peter, Laurence M ; Durrant, J R ; Yellowlees, L J ; Robertson, N. / Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells. In: European Journal of Inorganic Chemistry. 2011 ; Vol. 2011, No. 4. pp. 589-596.
@article{2dc96fc17c024dd589bcb87c5665cb5c,
title = "Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells",
abstract = "We prepared the complexes [Ru{4,4′-(CO2R-bpy)2}{Cu(exoO2-cyclam)}][NO3]2 [R = Et (1), H (2)], which possess a CuII centre covalently linked to a (bipyridyl)RuII fragment. The complexes were characterised by cyclic voltammetry, UV/Vis spectroscopy, hybrid DFT and TD-DFT (time-dependent density-functional theory) calculations, EPR (electron paramagnetic resonance), emission spectroscopy and UV/Vis spectroelectrochemistry, with the latter showing reversible conversion to the mono- and di-oxidised and mono- and di-reduced species. The data suggest the first oxidation to be largely based on the Ru centre but with little energetic difference between the highest occupied orbitals based on Ru and based on Cu. There was also evidence of solvent coordination in both the electrochemistry and spectroelectrochemistry experiments. The redox potentials and the strongvisible absorptions of 2 (λmax = 562 nm, ϵmax = 22200 M–1 cm–1)make it appropriate for study as a sensitiser in a dye-sensitised solar cell. Charge-separated lifetime of photoexcited 2 on TiO2 and incident photon-to-current conversion efficiency (IPCE) as a function of wavelength were studied and are discussed alongside the formation of dye-sensitised solar cells with the best efficiency achieved of η = 2.55 {\%}, Voc = 608 mV, Isc = 5.84 mA cm–2 and ff = 0.72. Limitations to the maximum efficiency obtained were attributed to a mismatch between the bipyridyl-based unoccupied orbital of the dye and the TiO2 conduction band edge.",
keywords = "copper, dye-sensitized solar cells, dinuclear complexes, supramolecular chemistry, ruthenium",
author = "McCall, {K L} and Jennings, {James R} and Wang, {H X} and A Morandeira and Peter, {Laurence M} and Durrant, {J R} and Yellowlees, {L J} and N Robertson",
year = "2011",
month = "2",
doi = "10.1002/ejic.201001039",
language = "English",
volume = "2011",
pages = "589--596",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
number = "4",

}

TY - JOUR

T1 - Dinuclear Ru-Cu Complexes: Electronic Characterisation and Application to Dye-Sensitised Solar Cells

AU - McCall, K L

AU - Jennings, James R

AU - Wang, H X

AU - Morandeira, A

AU - Peter, Laurence M

AU - Durrant, J R

AU - Yellowlees, L J

AU - Robertson, N

PY - 2011/2

Y1 - 2011/2

N2 - We prepared the complexes [Ru{4,4′-(CO2R-bpy)2}{Cu(exoO2-cyclam)}][NO3]2 [R = Et (1), H (2)], which possess a CuII centre covalently linked to a (bipyridyl)RuII fragment. The complexes were characterised by cyclic voltammetry, UV/Vis spectroscopy, hybrid DFT and TD-DFT (time-dependent density-functional theory) calculations, EPR (electron paramagnetic resonance), emission spectroscopy and UV/Vis spectroelectrochemistry, with the latter showing reversible conversion to the mono- and di-oxidised and mono- and di-reduced species. The data suggest the first oxidation to be largely based on the Ru centre but with little energetic difference between the highest occupied orbitals based on Ru and based on Cu. There was also evidence of solvent coordination in both the electrochemistry and spectroelectrochemistry experiments. The redox potentials and the strongvisible absorptions of 2 (λmax = 562 nm, ϵmax = 22200 M–1 cm–1)make it appropriate for study as a sensitiser in a dye-sensitised solar cell. Charge-separated lifetime of photoexcited 2 on TiO2 and incident photon-to-current conversion efficiency (IPCE) as a function of wavelength were studied and are discussed alongside the formation of dye-sensitised solar cells with the best efficiency achieved of η = 2.55 %, Voc = 608 mV, Isc = 5.84 mA cm–2 and ff = 0.72. Limitations to the maximum efficiency obtained were attributed to a mismatch between the bipyridyl-based unoccupied orbital of the dye and the TiO2 conduction band edge.

AB - We prepared the complexes [Ru{4,4′-(CO2R-bpy)2}{Cu(exoO2-cyclam)}][NO3]2 [R = Et (1), H (2)], which possess a CuII centre covalently linked to a (bipyridyl)RuII fragment. The complexes were characterised by cyclic voltammetry, UV/Vis spectroscopy, hybrid DFT and TD-DFT (time-dependent density-functional theory) calculations, EPR (electron paramagnetic resonance), emission spectroscopy and UV/Vis spectroelectrochemistry, with the latter showing reversible conversion to the mono- and di-oxidised and mono- and di-reduced species. The data suggest the first oxidation to be largely based on the Ru centre but with little energetic difference between the highest occupied orbitals based on Ru and based on Cu. There was also evidence of solvent coordination in both the electrochemistry and spectroelectrochemistry experiments. The redox potentials and the strongvisible absorptions of 2 (λmax = 562 nm, ϵmax = 22200 M–1 cm–1)make it appropriate for study as a sensitiser in a dye-sensitised solar cell. Charge-separated lifetime of photoexcited 2 on TiO2 and incident photon-to-current conversion efficiency (IPCE) as a function of wavelength were studied and are discussed alongside the formation of dye-sensitised solar cells with the best efficiency achieved of η = 2.55 %, Voc = 608 mV, Isc = 5.84 mA cm–2 and ff = 0.72. Limitations to the maximum efficiency obtained were attributed to a mismatch between the bipyridyl-based unoccupied orbital of the dye and the TiO2 conduction band edge.

KW - copper

KW - dye-sensitized solar cells

KW - dinuclear complexes

KW - supramolecular chemistry

KW - ruthenium

UR - http://www.scopus.com/inward/record.url?scp=79251581031&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1002/ejic.201001039

U2 - 10.1002/ejic.201001039

DO - 10.1002/ejic.201001039

M3 - Article

VL - 2011

SP - 589

EP - 596

JO - European Journal of Inorganic Chemistry

T2 - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 4

ER -