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The versatile SALSAC approach to heteroleptic copper(I) dye assembly in dye-sensitized solar cells

Malzner, Frederik J. and Housecroft, Catherine E. and Constable, Edwin C.. (2018) The versatile SALSAC approach to heteroleptic copper(I) dye assembly in dye-sensitized solar cells. Inorganics, 6 (2). p. 57.

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Abstract

Surface-bound heteroleptic copper(I) dyes [Cu(L anchor )(L ancillary )] + 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/TiO 2 electrode is functionalized with 3 in the first dye bath, and then undergoes ligand exchange with the homoleptic complex [Cu( 4 ) 2 ][PF 6 ] to give surface-bound [Cu( 3 )( 4 )] + . In the second method, the FTO/TiO 2 electrode functionalized with 3 is immersed in a solution containing a 1 : 1 mixture of [Cu(MeCN) 4 ][PF 6 ] 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 J SC (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 ][PF 6 ] and 4 yields DSSCs with higher V OC values but lower J SC 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 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(L ancillary ) 2 ] + is difficult or time-consuming; stepwise strategies are more atom-economic than ligand exchange involving the homoleptic [Cu(L ancillary ) 2 ] + .
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:MDPI
e-ISSN:2304-6740
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:04 Jul 2018 11:00
Deposited On:04 Jul 2018 11:00

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