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Are Alkynyl Spacers in Ancillary Ligands in Heteroleptic Bis(diimine)copper(I) Dyes Beneficial for Dye Performance in Dye-Sensitized Solar Cells?

Risi, Guglielmo and Becker, Mariia and Housecroft, Catherine E. and Constable, Edwin C.. (2020) Are Alkynyl Spacers in Ancillary Ligands in Heteroleptic Bis(diimine)copper(I) Dyes Beneficial for Dye Performance in Dye-Sensitized Solar Cells? Molecules, 25. p. 1528.

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Abstract

The syntheses of 4,40 -bis(4-dimethylaminophenyl)-6,60 -dimethyl-2,20 -bipyridine (1 ), 4,40 -bis(4-dimethylaminophenylethynyl)-6,60 -dimethyl-2,20 -bipyridine (2 ), 4,40 -bis(4- diphenylaminophenyl)-6,60 -dimethyl-2,20 -bipyridine (3 ), and 4,40 -bis(4-diphenylaminophenylethynyl)- 6,60 -dimethyl-2,20 -bipyridine (4 ) are reported along with the preparations and characterisations of their homoleptic copper(I) complexes [CuL2 ][PF6 ] (L = 1 -4 ). The solution absorption spectra of the complexes exhibit ligand-centred absorptions in addition to absorptions in the visible region assigned to a combination of intra-ligand and metal-to-ligand charge-transfer. Heteroleptic [Cu(5 )(Lancillary )]+ dyes in which 5 is the anchoring ligand ((6,60 -dimethyl-[2,20 -bipyridine]- 4,40 -diyl)bis(4,1-phenylene))bis(phosphonic acid) and Lancillary = 1 -4 have been assembled on fluorine-doped tin oxide (FTO)-TiO2 electrodes in dye-sensitized solar cells (DSCs). Performance parameters and external quantum e ciency (EQE) spectra of the DSCs (four fully-masked cells for each dye) reveal that the best performing dyes are [Cu(5 )(1 )]+ and [Cu(5 )(3 )]+ . The alkynyl spacers are not beneficial, leading to a decrease in the short-circuit current density (JSC ), confirmed by lower values of EQEmax . Addition of a co-absorbent (n -decylphosphonic acid) to [Cu(5 )(1 )]+ lead to no significant enhancement of performance for DSCs sensitized with [Cu(5 )(1 )]+ . Electrochemical impedance spectroscopy (EIS) has been used to investigate the interfaces in DSCs; the analysis shows that more favourable electron injection into TiO2 is observed for sensitizers without the alkynyl spacer and confirms higher JSC values for [Cu(5 )(1 )]+
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 and Constable, Edwin Charles and Becker, Mariia and Risi, Guglielmo
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:MDPI
e-ISSN:1420-3049
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
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Last Modified:01 Apr 2020 08:22
Deposited On:01 Apr 2020 08:22

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