Browsing by Author "Schwalbe, Matthias"

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    Exploring the full potential of photocatalytic carbon dioxide reduction using a dinuclear Re2Cl2 complex assisted by various photosensitizers
    (2021) Giereth, Robin; Obermeier, Martin; Forschner, Lukas; Karnahl, Michael; Schwalbe, Matthias; Tschierlei, Stefanie
    Photosensitizing units have already been applied to enable light‐driven catalytic reduction of CO2 with mononuclear rhenium complexes. However, dinuclear catalytic systems that are able to activate CO2 in a cooperative bimetallic fashion have only rarely been combined with photosensitizers. We here present detailed studies on the influence of additional photosensitizers on the catalytic performance of a dirhenium complex (Re2Cl2) and present correlations with spectroscopic measurements, which shed light on the reaction mechanism. The use of [Ir(dFppy)3] (Ir, dFppy=2‐(4,6‐difluorophenyl)pyridine)) resulted in considerably faster CO2 to CO transformation than [Cu(xant)(bcp)]PF6 (Cu, xant=xantphos, bcp=bathocuproine). Emission quenching studies, transient absorption as well as IR spectroscopy provide information about the electron transfer paths of the intermolecular systems. It turned out that formation of double reduced species [Re2Cl2]2- along with an intermediate with a Re-Re bond ([ReRe]) can be taken as an indication of multi‐electron storage capacity. Furthermore, under catalytic conditions a CO2‐bridged intermediate was identified.