title: Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers.
abstract: It is successfully shown that photocatalytic proton reduction to dihydrogen in the presence of a sacrificial electron donor, such as trimethylamine (TEA) and ascorbate, can be driven by compact sensitizer-catalyst dyads, that is, dithiolate-bridged [FeFe] hydrogenase models tethered to organic sensitizers, such as fluorenes and silafluorenes (1 a-4 a). The sensitizer-catalyst dyads 1 a-4 a show remarkable and promising catalytic activities as well as enhanced stabilities during photocatalysis performed under UV-light irradiation. The photocatalysis was carried out both in non-aqueous and aqueous media. The latter experiments were performed by solubilizing the photocatalysts within micelles formed by either sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB). In this study a turnover number of 539 (7 h) is achieved under optimized conditions, which corresponds to an exceptionally high turnover frequency of 77 h-1. Theoretical investigations as well as emission decay experiments were performed to understand the observed phenomena together with the mechanisms of photocatalytic H2generation.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, Humboldtstraße 8, 07743, Jena, Germany.
authors.forename: Roman
authors.initials: R
authors.lastname: Goy
authors.affiliation: Department of Biotechnology and Biosciences, University of Milano-Bicocca, 20126, Milan, Italy.
authors.forename: Luca
authors.initials: L
authors.lastname: Bertini
authors.affiliation: Institut für Organische Chemie und Makromolekulare Chemie (IOMC) and Jena Center for Soft Matter (JCSM), Friedrich-Schiller-Universität Jena, Lessingstraße 8, 07743, Jena, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Rudolph
authors.affiliation: Department of Chemistry, Faculty of Science, and International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Motooka 744, Nishi-ku, Fukuoka, 819-0395, Japan.
authors.forename: Shu
authors.initials: S
authors.lastname: Lin
authors.affiliation: Institut für Physikalische Chemie, Friedrich-Schiller-Universität, Helmholtzweg 4, 07743, Jena, Germany.|Abteilung Funktionale Grenzflächen, Leibniz-Institut für Photonische Technologien, Albert-Einstein-Str. 9, 07745, Jena, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Schulz
authors.affiliation: Department of Biotechnology and Biosciences, University of Milano-Bicocca, 20126, Milan, Italy.
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Zampella
authors.affiliation: Institut für Physikalische Chemie, Friedrich-Schiller-Universität, Helmholtzweg 4, 07743, Jena, Germany.|Abteilung Funktionale Grenzflächen, Leibniz-Institut für Photonische Technologien, Albert-Einstein-Str. 9, 07745, Jena, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Dietzek
authors.affiliation: Institut für Organische Chemie und Makromolekulare Chemie (IOMC) and Jena Center for Soft Matter (JCSM), Friedrich-Schiller-Universität Jena, Lessingstraße 8, 07743, Jena, Germany.
authors.forename: Felix H
authors.initials: FH
authors.lastname: Schacher
authors.affiliation: Department of Biotechnology and Biosciences, University of Milano-Bicocca, 20126, Milan, Italy.
authors.forename: Luca
authors.initials: L
authors.lastname: De Gioia
authors.affiliation: Department of Chemistry, Faculty of Science, and International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Motooka 744, Nishi-ku, Fukuoka, 819-0395, Japan.
authors.forename: Ken
authors.initials: K
authors.lastname: Sakai
authors.affiliation: Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität, Humboldtstraße 8, 07743, Jena, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Weigand
keywords: density functional calculations; hydrogen; hydrogenases; micelles; photocatalysis