NDLI: Halos show the path to perfection: peripheral iodo-substituents improve the efficiencies of bis(diimine)copper(i) dyes in DSCs

Content Provider	Royal Society of Chemistry (RSC)
Author	Constable, Edwin C. Brauchli, Sven Y. Housecroft, Catherine E. Neuburger, Markus Malzner, Frederik J.
Copyright Year	2014
Abstract	The homoleptic copper(I) complexes [CuL2][PF6] (L = 4,4′-bis(4-halophenyl)-6,6′-dimethyl-2,2′-bipyridine with halogen = F (2) and Cl (3)) have been prepared and characterized, and their absorption spectroscopic and electrochemical properties compared to that with L = 4,4′-bis(4-bromophenyl)-6,6′-dimethyl-2,2′-bipyridine (4). The synthesis of [CuL2][PF6] (L = 4,4′-bis(4-iodophenyl)-6,6′-dimethyl-2,2′-bipyridine, 5) resulted in a mixture of [Cu(5)2][PF6] and [Cu(5)(MeCN)2][PF6]; variable temperature 1H NMR spectroscopy confirmed that the complexes are in equilibrium in CD3CN solution. The structure of [Cu(5)(MeCN)2][PF6] was determined by single crystal X-ray crystallography, and confirms a distorted tetrahedral geometry for the copper(I) centre. The heteroleptic dyes [Cu(1)(2)]+, [Cu(1)(3)]+, [Cu(1)(4)]+ and [Cu(1)(5)]+ (1 = ((6,6′-dimethyl-[2,2′-bipyridine]-4,4′-diyl)bis(4,1-phenylene))bis(phosphonic acid)) have been assembled by ligand exchange between [CuL2]+ and TiO2 functionalized with the anchoring ligand 1, and the performances of the dyes in fully masked dye-sensitized solar cells (DSCs) have been measured and compared. On the day of DSC fabrication, the trend for the global efficiencies, η, depends on the halo-substituent in the order I > F ≈ Br > Cl. Ripening of the DSCs occurs and after 7 days, the dependence of η on the halo-atom is in the order I > Cl ≈ F ≈ Br; the highest η is 3.16% for [Cu(1)(5)]+ compared to 7.63% for N719. Compared to the other halo-functionalized dyes, [Cu(1)(5)]+ shows an extended spectral response to longer wavelength, with enhanced electron injection. The results of DFT calculations suggest that the better dye performance of [Cu(1)(5)]+ may be associated with improved electron transfer over the halogen of the aryl substituent from the reduced electrolyte. The assembly of anchored dye [Cu(1)(5)]+ by treating functionalized-TiO2 with a 1 : 1 mixture of [Cu(MeCN)4]+ and 5, yields a dye which gives a DSC performance that matches that made by ligand exchange using [Cu(5)2][PF6] and [Cu(5)(MeCN)2][PF6].
Starting Page	48712
Ending Page	48723
Page Count	12
File Format	HTM / HTML PDF
ISSN	20462069
Volume Number	4
Issue Number	89
Journal	RSC Advances
DOI	10.1039/c4ra06823h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Dye-sensitized solar cell Aromaticity Ligand CUL2 Nuclear magnetic resonance spectroscopy Substituent Wavelength Molecular geometry X-ray crystallography Dye Electrolyte DSC Carboxylic acid Bipyridine Homoleptic Halogen Electrochemistry Copper Correlation and dependence
Content Type	Text
Resource Type	Article
Subject	Chemistry Chemical Engineering

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Halos show the path to perfection: peripheral iodo-substituents improve the efficiencies of bis(diimine)copper(I) dyes in DSCs

ath to perfection : peripheral iodo-substituents improve the e ffi ciencies of bis ( diimine ) copper ( I ) dyes in DSCs †

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Halos show the path to perfection: peripheral iodo-substituents improve the efficiencies of bis(diimine)copper(i) dyes in DSCs

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Halos show the path to perfection: peripheral iodo-substituents improve the efficiencies of bis(diimine)copper(i) dyes in DSCs