Tetracoordinated Bis-phenanthroline Copper-Complex Couple as Efficient Redox Mediators for Dye Solar Cells. Magni, M., Giannuzzi, R., Colombo, A., Cipolla, M. P., Dragonetti, C., Caramor, S., Carli, S., Grisorio, R., Suranna, G. P., Bignozzi, C. A., Roberto, D., & Manca, M. INORGANIC CHEMISTRY, 55(11):5245-5253, JUN 6, 2016.
doi  abstract   bibtex   
A tetracoordinated redox couple, made by [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)(2)][PF6], 1, and its Cu(II) form [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)(2)] [PF6](2), 2, has been synthesized, and its electrochemical and photochemical features have been investigated and compared with those of a previously published Cu2+/Cu+ redox shuttle, namely, [Cu(2,9-dimethyl-1,10-phenanthroline)(2)][PF6], 3, and its pentacoordinated oxidized form [Cu(2,9-dimethyl-1,10-phenanthroline)(2)Cl][PF6], 4. The detrimental effect of the fifth Cl- ancillary ligand on the charge transfer kinetics of the redox shuttles has been exhaustively demonstrated. Appropriately balanced Cu-based electrolytes have been then formulated and tested in dye solar cells in combination with a pi-extended benzothiadiazole dye. The bisphenanthroline Cu-complexes, 1 and 2, have been found to provide an overall 4.4% solar energy conversion efficiency, which is more than twice that of the literature benchmark couple, 3 and 4, employing a Cl-coordinated oxidized species and even comparable with the performances of a I-/I-3(-) electrolyte of analogous concentration. A fast counter-electrode reaction, due to the excellent electrochemical reversibility of 2, and a high electron collection efficiency, allowed through the efficient dye regeneration kinetics exerted by 1, represents two major characteristics of these copper-based electron mediators and may constitute a pivotal step toward the development of a next generation of copper-based efficient iodine-free redox shuttles.
@article{ ISI:000377151000022,
Author = {Magni, Mirko and Giannuzzi, Roberto and Colombo, Alessia and Cipolla,
   Maria Pia and Dragonetti, Claudia and Caramor, Stefano and Carli,
   Stefano and Grisorio, Roberto and Suranna, Gian Paolo and Bignozzi,
   Carlo Alberto and Roberto, Dominique and Manca, Michele},
Title = {{Tetracoordinated Bis-phenanthroline Copper-Complex Couple as Efficient
   Redox Mediators for Dye Solar Cells}},
Journal = {{INORGANIC CHEMISTRY}},
Year = {{2016}},
Volume = {{55}},
Number = {{11}},
Pages = {{5245-5253}},
Month = {{JUN 6}},
Abstract = {{A tetracoordinated redox couple, made by
   {[}Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)(2)]{[}PF6], 1, and its
   Cu(II) form {[}Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)(2)]
   {[}PF6](2), 2, has been synthesized, and its electrochemical and
   photochemical features have been investigated and compared with those of
   a previously published Cu2+/Cu+ redox shuttle, namely,
   {[}Cu(2,9-dimethyl-1,10-phenanthroline)(2)]{[}PF6], 3, and its
   pentacoordinated oxidized form
   {[}Cu(2,9-dimethyl-1,10-phenanthroline)(2)Cl]{[}PF6], 4. The detrimental
   effect of the fifth Cl- ancillary ligand on the charge transfer kinetics
   of the redox shuttles has been exhaustively demonstrated. Appropriately
   balanced Cu-based electrolytes have been then formulated and tested in
   dye solar cells in combination with a pi-extended benzothiadiazole dye.
   The bisphenanthroline Cu-complexes, 1 and 2, have been found to provide
   an overall 4.4\% solar energy conversion efficiency, which is more than
   twice that of the literature benchmark couple, 3 and 4, employing a
   Cl-coordinated oxidized species and even comparable with the
   performances of a I-/I-3(-) electrolyte of analogous concentration. A
   fast counter-electrode reaction, due to the excellent electrochemical
   reversibility of 2, and a high electron collection efficiency, allowed
   through the efficient dye regeneration kinetics exerted by 1, represents
   two major characteristics of these copper-based electron mediators and
   may constitute a pivotal step toward the development of a next
   generation of copper-based efficient iodine-free redox shuttles.}},
DOI = {{10.1021/acs.inorgchem.6b00204}},
ISSN = {{0020-1669}},
EISSN = {{1520-510X}},
ResearcherID-Numbers = {{Dragonetti, Claudia/Q-4366-2016
   Manca, Michele/O-8468-2015
   Carli, Stefano/B-7085-2015
   Roberto, Dominique/R-3011-2016
   Magni, Mirko/U-5936-2017
   Colombo, Alessia/Q-4413-2016
   }},
ORCID-Numbers = {{Dragonetti, Claudia/0000-0002-0106-0860
   Manca, Michele/0000-0002-6903-2954
   Carli, Stefano/0000-0002-0309-2356
   Roberto, Dominique/0000-0001-9659-4760
   Magni, Mirko/0000-0001-9776-2973
   Colombo, Alessia/0000-0001-8004-3200
   Giannuzzi, Roberto/0000-0002-0997-5686
   SURANNA, Gian Paolo/0000-0003-2953-0809
   Grisorio, Roberto/0000-0002-3698-9370}},
Unique-ID = {{ISI:000377151000022}},
}
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