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Authors: Moll, Johannnes
Wang, Cui
Päpcke, Ayla
Förster, Christoph
Resch-Genger, Ute
Lochbrunner, Stefan
Heinze, Katja
Title: Green-light activation of push–pull ruthenium(II) complexes
Online publication date: 9-Aug-2021
Language: english
Abstract: Synthesis, characterization, electrochemistry, and photophysics of homo- and heteroleptic ruthenium(II) complexes [Ru(cpmp)2]2+ (22+) and [Ru(cpmp)(ddpd)]2+ (32+) bearing the tridentate ligands 6,2’’-carboxypyridyl-2,2’-methylamine-pyridyl-pyridine (cpmp) and N,N’-dimethyl-N,N’-dipyridin-2-ylpyridine-2,6-diamine (ddpd) are reported. The complexes possess one (32+) or two (22+) electron-deficient dipyridyl ketone fragments as electron-accepting sites enabling intraligand charge transfer (ILCT), ligand-to-ligand charge transfer (LL'CT) and low-energy metal-to-ligand charge transfer (MLCT) absorptions. The latter peak around 544 nm (green light). Complex 22+ shows 3MLCT phosphorescence in the red to near-infrared spectral region at room temperature in deaerated acetonitrile solution with an emission quantum yield of 1.3 % and a 3MLCT lifetime of 477 ns, whereas 32+ is much less luminescent. This different behavior is ascribed to the energy gap law and the shape of the parasitic excited 3MC state potential energy surface. This study highlights the importance of the excited-state energies and geometries for the actual excited-state dynamics. Aromatic and aliphatic amines reductively quench the excited state of 22+ paving the way to photocatalytic applications using low-energy green light as exemplified with the green-light-sensitized thiol–ene click reaction.
DDC: 540 Chemie
540 Chemistry and allied sciences
Institution: Johannes Gutenberg-Universität Mainz
Department: FB 09 Chemie, Pharmazie u. Geowissensch.
Place: Mainz
Version: Published version
Publication type: Zeitschriftenaufsatz
License: CC BY
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Journal: Chemistry - a European journal
Pages or article number: 6820
Publisher: Wiley-VCH
Publisher place: Weinheim
Issue date: 2020
ISSN: 1521-3765
Publisher URL:
Publisher DOI: 10.1002/chem.202000871
Appears in collections:JGU-Publikationen

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