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.

Tetracoordinated Bis-phenanthroline Copper-Complex Couple as Efficient Redox Mediators for Dye Solar Cells

CARAMORI, Stefano;CARLI, Stefano;BIGNOZZI, Carlo Alberto;
2016

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.
Magni, M.; Giannuzzi, R.; Colombo, A.; Cipolla, Mp; Dragonetti, C; Caramori, Stefano; Carli, Stefano; Grisorio, R; Suranna, Gp; Bignozzi, Carlo Alberto; Roberto, D; Manca, M.
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