title: Heteroleptic Ru(ii)-bipyridine complexes based on hexylthioether-, hexyloxy- and hexyl-substituted thienylenevinylenes and their application in dye-sensitized solar cells.
abstract: A series of eight Ru(ii) heteroleptic complexes incorporating an ancillary [2,2']bipyridine functionalised at the [4,4'] positions with one (-type) or two (-type) thienylenevinylenes (nTVs, n = 2 or 4) is reported. Three types of substitutions have been used for nTVs: hexylthioether, hexyloxy and hexyl. The characterisation of the half-sandwich intermediates and final complexes is provided. In particular, the half-sandwich complexes in the -type series are obtained as a racemate, whereas the heteroleptic complexes consist of two regioisomers. Finally, these complexes have been tested as dyes in dye-sensitized solar cells (DSSCs). Counterintuitively, better performances were obtained for -type complexes with shorter 2TV moieties. The best performing dye was the Ru(ii) complex mono-functionalized with a 2TV moiety having an hexylthioether substitution (), which achieved a maximum power efficiency of 2.77% under full sun illumination (AM1.5G standard conditions). The structure-performance relationship in DSSCs is discussed based on photovoltaic and electrochemical data and DFT-calculations.
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. maxence.urbani@uam.es tomas.torres@uam.es and Instituto de Nanociencia, Nanotecnología y Materiales Moleculares (INAMOL) Universidad de Castilla-La Mancha, Campus de la Fábrica de Armas, 45071 Toledo, Spain. fernando.langa@uclm.es and Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, Swiss Federal Institute of Technology (EPFL), Station 6, CH 1015 - Lausanne, Switzerland. mdkhaja.nazeeruddin@epfl.ch and Instituto Madrileño de Estudios Avanzados (IMDEA)-Nanociencia c/Faraday, 9, Cantoblanco, 28049 Madrid, Spain.
authors.forename: Maxence
authors.initials: M
authors.lastname: Urbani
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. maxence.urbani@uam.es tomas.torres@uam.es.
authors.forename: María
authors.initials: M
authors.lastname: Sánchez Carballo
authors.affiliation: Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, Swiss Federal Institute of Technology (EPFL), Station 6, CH 1015 - Lausanne, Switzerland. mdkhaja.nazeeruddin@epfl.ch.
authors.forename: Sangeeta Amit
authors.initials: SA
authors.lastname: Kumar
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. maxence.urbani@uam.es tomas.torres@uam.es.
authors.forename: Purificación
authors.initials: P
authors.lastname: Vázquez
authors.affiliation: Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, Swiss Federal Institute of Technology (EPFL), Station 6, CH 1015 - Lausanne, Switzerland. mdkhaja.nazeeruddin@epfl.ch.
authors.forename: Michael
authors.initials: M
authors.lastname: Grätzel
authors.affiliation: Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, Swiss Federal Institute of Technology (EPFL), Station 6, CH 1015 - Lausanne, Switzerland. mdkhaja.nazeeruddin@epfl.ch and Group for Molecular Engineering of Functional materials, Institute of Chemical Sciences and Engineering Swiss Federal Institute of Technology (EPFL), Valais Wallis, Rue de l'Indutrie 17, CH 1950 - Sion, Valais, Switzerland.
authors.forename: Mohammad
authors.initials: M
authors.lastname: Khaja Nazeeruddin
authors.affiliation: Instituto de Nanociencia, Nanotecnología y Materiales Moleculares (INAMOL) Universidad de Castilla-La Mancha, Campus de la Fábrica de Armas, 45071 Toledo, Spain. fernando.langa@uclm.es.
authors.forename: Fernando
authors.initials: F
authors.lastname: Langa
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. maxence.urbani@uam.es tomas.torres@uam.es and Instituto Madrileño de Estudios Avanzados (IMDEA)-Nanociencia c/Faraday, 9, Cantoblanco, 28049 Madrid, Spain.
authors.forename: Tomás
authors.initials: T
authors.lastname: Torres