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Article

The Versatile SALSAC Approach to Heteroleptic Copper(I) Dye Assembly in Dye-Sensitized Solar Cells

Department of Chemistry, University of Basel, Building 1096, Mattenstrasse 24a, CH-4058 Basel, Switzerland
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Author to whom correspondence should be addressed.
Received: 8 May 2018 / Revised: 23 May 2018 / Accepted: 23 May 2018 / Published: 25 May 2018
(This article belongs to the Collection Coordination Complexes for Dye-Sensitized Solar Cells (DSCs))
Surface-bound heteroleptic copper(I) dyes [Cu(Lanchor)(Lancillary)]+ are assembled using the “surfaces-as-ligands, surfaces as complexes” (SALSAC) approach by three different procedures. The anchoring and ancillary ligands chosen are ((6,6′-dimethyl-[2,2′-bipyridine]-4,4′-diyl)-bis(4,1-phenylene))bis(phosphonic acid) (3) and 4,4′-bis(4-iodophenyl)-6,6′-diphenyl-2,2′-bipyridine (4), respectively. In the first SALSAC procedure, the FTO/TiO2 electrode is functionalized with 3 in the first dye bath, and then undergoes ligand exchange with the homoleptic complex [Cu(4)2][PF6] to give surface-bound [Cu(3)(4)]+. In the second method, the FTO/TiO2 electrode functionalized with 3 is immersed in a solution containing a 1:1 mixture of [Cu(MeCN)4][PF6] and 4 to give surface-anchored [Cu(3)(4)]+. In the third procedure, the anchor 3, copper(I) ion and ancillary ligand 4 are introduced in a sequential manner. The performances of the DSSCs show a dependence on the dye assembly procedure. The sequential method leads to the best-performing DSSCs with the highest values of JSC (7.85 and 7.73 mA cm−2 for fully masked cells) and overall efficiencies (η = 2.81 and 2.71%, representing 41.1 and 39.6% relative to an N719 reference DSSC). Use of the 1:1 mixture of [Cu(MeCN)4][PF6] and 4 yields DSSCs with higher VOC values but lower JSC values compared to those assembled using the sequential approach; values of η are 2.27 and 2.29% versus 6.84% for the N719 reference DSSC. The ligand exchange procedure leads to DSSCs that perform relatively poorly. The investigation demonstrates the versatile and powerful nature of SALSAC in preparing dyes for copper-based DSSCs, allowing the photoconversion efficiency of dye to be optimized for a given dye. The SALSAC strategy provides alternative hierarchical strategies where the isolation of the homoleptic [Cu(Lancillary)2]+ is difficult or time-consuming; stepwise strategies are more atom-economic than ligand exchange involving the homoleptic [Cu(Lancillary)2]+. View Full-Text
Keywords: copper; 2,2′-bipyridine; dye-sensitized solar cell; solar energy conversion; iodo-substitution; stepwise surface dye assembly copper; 2,2′-bipyridine; dye-sensitized solar cell; solar energy conversion; iodo-substitution; stepwise surface dye assembly
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MDPI and ACS Style

Malzner, F.J.; Housecroft, C.E.; Constable, E.C. The Versatile SALSAC Approach to Heteroleptic Copper(I) Dye Assembly in Dye-Sensitized Solar Cells. Inorganics 2018, 6, 57. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics6020057

AMA Style

Malzner FJ, Housecroft CE, Constable EC. The Versatile SALSAC Approach to Heteroleptic Copper(I) Dye Assembly in Dye-Sensitized Solar Cells. Inorganics. 2018; 6(2):57. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics6020057

Chicago/Turabian Style

Malzner, Frederik J., Catherine E. Housecroft, and Edwin C. Constable. 2018. "The Versatile SALSAC Approach to Heteroleptic Copper(I) Dye Assembly in Dye-Sensitized Solar Cells" Inorganics 6, no. 2: 57. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics6020057

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