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Modular synthesis of simple cycloruthenated complexes with state-of-the-art performance in p-type DSCs

Brunner, Felix and Marinakis, Nathalie and Wobill, Cederic and Willgert, Markus and Ertl, Cathrin D. and Kosmalski, Tatjana and Neuburger, Markus and Bozic-Weber, Biljana and Glatzel, Thilo and Constable, Edwin C. and Housecroft, Catherine E.. (2016) Modular synthesis of simple cycloruthenated complexes with state-of-the-art performance in p-type DSCs. Journal of Materials Chemistry C, 4 (41). pp. 9823-9833.

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Abstract

A modular approach based on Suzuki-Miyaura cross coupling and Miyaura borylation has been used to prepare two cyclometallated [Ru(N^N) 2 (C^N)] + complexes which possess either a carboxylic or phosphonic acid group attached via a phenylene spacer to the 4-position of the pyridine ring in the C^N ligand. The key intermediate in the synthetic pathway is [Ru(bpy) 2 ( 1 )] + where bpy = 2,2'-bipyridine and H 1 is 4-chloro-2-phenylpyridine. The crystal structure of [Ru(bpy) 2 ( 1 )][PF 6 ] is presented. Reaction of [Ru(bpy) 2 ( 1 )][PF 6 ] with 4-carboxyphenylboronic acid leads to [Ru(bpy) 2 (H 6 )][PF 6 ], while the phosphonic acid analogue is isolated as the zwitterion [Ru(bpy) 2 (H 5 )]. The cyclometallated complexes have been characterized by mass spectrometry, multinuclear NMR spectroscopy, absorption spectroscopy and electrochemistry. [Ru(bpy) 2 ( 5 )] adsorbs onto NiO FTO/NiO electrodes (confirmed by solid-state absorption spectroscopy) and its performance in p-type dye-sensitized solar cells (DSCs) has been compared to that of the standard dye P1; two-screen printed layers of NiO give better DSC performances than one layer. Duplicate DSCs containing [Ru(bpy) 2 (H 5 )] achieve short-circuit current densities ( J SC ) of 3.38 and 3.34 mA cm –2 and photoconversion efficiencies ( η ) of 0.116 and 0.109%, respectively, compared to values of J SC = 1.84 and 1.96 mA cm –2 and η = 0.057 and 0.051% for P1. Despite its simple dye structure, the performance of [Ru(bpy) 2 (H 5 )] parallels the best-performing cyclometallated ruthenium(II) dye in p-type DSCs reported previously (He et al , J. Phys. Chem. C , 2014, 118 , 16518) and confirms the effectiveness of a phosphonic acid anchor in the dye and the attachment of the anchoring unit to the pyridine (rather than phenyl) ring of the cyclometallating ligand
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 Brunner, Felix and Marinakis, Nathalie and Wobill, Cedric and Neuburger, Markus and Willgert, Markus and Ertl, Cathrin and Kosmalski, Tatjana and Bozic Weber, Biljana and Glatzel, Thilo
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
ISSN:2050-7534
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:14 Nov 2016 09:39
Deposited On:14 Nov 2016 09:39

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