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