Dr. Matthias Schwalbe forscht auf dem Gebiet der molekularen Katalyse, insbesondere zur licht- und elektrogetriebenen Aktivierung kleiner Moleküle wie CO2 und Wasser. Sein Fokus liegt auf der Synthese und mechanistischen Aufklärung heterodinuklearer Metallkomplexe, darunter Hangman-Porphyrine und Hetero-Pacman-Verbindungen. Er nutzt spektroelektrochemische Methoden, insbesondere Raman-Spektroskopie, um Struktur-Aktivitäts-Beziehungen unter Reaktionsbedingungen zu untersuchen. Die Arbeit zielt darauf ab, effiziente Katalysatorsysteme für die Energieumwandlung und nachhaltige chemische Produktion zu entwickeln.
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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 Exzellenzinitiative Cluster Zeitraum: 11/2017 - 12/2018 Projektleitung: Prof. Dr. Athina Zouni
Förderer: DFG Exzellenzstrategie Cluster Zeitraum: 01/2019 - 12/2025 Projektleitung: Prof. Dr. Arne Thomas
Förderer: DFG Exzellenzstrategie Cluster Zeitraum: 01/2019 - 03/2022 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.