Dr. Matthias Schwalbe erforscht molekulare Metallkatalysatoren für energiewirtschaftliche Umwandlungsprozesse — insbesondere die lichtgetriebene Wasserspaltung, CO₂-Reduktion und Wasserstoffproduktion. Sein aktueller Fokus liegt auf heterodinuklearen Komplexen (sogenannte Pacman- und Hangman-Porphyrine), deren katalytische Aktivität er durch spektroelektrochemische Methoden in situ untersucht, um die Reaktionsmechanismen auf molekularer Ebene zu verstehen. Diese Erkenntnisse ermöglichen die rationale Optimierung von Katalysatoren für die Wasserstoff- und Chemikalienproduktion aus erneuerbaren Energiequellen. Die Arbeiten sind relevant für die Chemie- und Energieindustrie sowie für Anwendungen in künstlicher Photosynthese und Elektrokatalyse.
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Dr. Matthias Schwalbe
HU-FIS-Profil ↗EXC 2008: Unifying Systems in Catalysis (UniSysCat)
university
EXC 2008: Unifying Systems in Catalysis (UniSysCat)
university
EXC 2008: Unifying Systems in Catalysis (UniSysCat)
other
Förderer: DFG Eigene Stelle (Sachbeihilfe) Zeitraum: 06/2010 - 06/2014 Projektleitung: Dr. Matthias Schwalbe
Förderer: DFG Exzellenzinitiative Cluster Zeitraum: 11/2012 - 10/2017 Projektleitung: Dr. Matthias Schwalbe
Förderer: DFG Eigene Stelle (Sachbeihilfe) Zeitraum: 08/2013 - 12/2017 Projektleitung: Dr. Matthias Schwalbe
Journal of the American Chemical Society · DOI
The construction of a new class of compounds--the hangman corroles--is provided efficiently by the modification of macrocyclic forming reactions from bilanes. Hangman cobalt corroles are furnished in good yields from a one-pot condensation of dipyrromethane with the aldehyde of a xanthene spacer followed by metal insertion using microwave irradiation. In high oxidation states, X-band EPR spectra and DFT calculations of cobalt corrole axially ligated by chloride are consistent with the description of a Co(III) center residing in the one-electron oxidized corrole macrocycle. These high oxidation states are likely accessed in the activation of O-O bonds. Along these lines, we show that the proton-donating group of the hangman platform works in concert with the redox properties of the corrole to enhance the catalytic activity of O-O bond activation. The hangman corroles show enhanced activity for the selective reduction of oxygen to water as compared to their unmodified counterparts. The oxygen adduct, prior to oxygen reduction, is characterized by EPR and absorption spectroscopy.
Coordination Chemistry Reviews · DOI
Chemistry - A European Journal · DOI
Photoinduced electron-transfer processes within a precatalyst for intramolecular hydrogen evolution [(tbbpy)(2)Ru(tpphz)PdCl(2)](2+) (RuPd; tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine, tpphz = tetrapyrido[3,2-a:2',3'c:3'',2'',-h:2''',3'''-j]phenazine) have been studied by resonance Raman and ultrafast time-resolved absorption spectroscopy. By comparing the photophysics of the [(tbbpy)(2)Ru(tpphz)](2+) subunit Ru with that of the supramolecular catalyst RuPd, the individual electron-transfer steps are assigned to kinetic components, and their dependence on solvent is discussed. The resonance Raman data reveal that the initial excitation of the molecular ensemble is spread over the terminal tbbpy and the tpphz ligands. The subsequent excited-state relaxation of both Ru and RuPd on the picosecond timescale involves formation of the phenazine-centered intraligand charge-transfer state, which in RuPd precedes formation of the Pd-reduced state. The photoreaction in the heterodinuclear supramolecular complex is completed on a subnanosecond timescale. Taken together, the data indicate that mechanistic investigations must focus on potential rate-determining steps other than electron transfer between the photoactive center and the Pd unit. Furthermore, structural variations should be directed towards increasing the directionality of electron transfer and the stability of the charge-separated states.