Exploiting the Disulfide/Thiol Switch for Photoinduced Proton-Coupled Multielectron Transfer Reactivity

Oelschlegel, Manuel

dc.contributor.advisor	Meyer, Franc Prof. Dr.
dc.contributor.author	Oelschlegel, Manuel
dc.date.accessioned	2024-03-27T13:29:23Z
dc.date.issued	2024-03-27
dc.identifier.uri	http://resolver.sub.uni-goettingen.de/purl?ediss-11858/15186
dc.identifier.uri	http://dx.doi.org/10.53846/goediss-10422
dc.format.extent	220	de
dc.language.iso	eng	de
dc.subject.ddc	540	de
dc.title	Exploiting the Disulfide/Thiol Switch for Photoinduced Proton-Coupled Multielectron Transfer Reactivity	de
dc.type	doctoralThesis	de
dc.contributor.referee	Meyer, Franc Prof. Dr.
dc.date.examination	2024-02-29	de
dc.description.abstracteng	Energy storage and efficient release has become a pivotal issue for our society relying progressively on renewable energy sources. The dichotomy between harvesting the sun’s energy in daylight hours, and requiring it the most during nighttime, produces the need for prolonged energy storage. Herein, molecular systems capable of performing a reversible single-photon triggered proton-coupled multi-electron transfer (PCET) are established. To achieve accumulation of two electrons from their photo-excited states and their decoupled release in the absence of light, the potential inversion of a disulfide/thiol redox switch is exploited. Assembly of the light harvesting and charge relay unit in one molecular system is accomplished by the combination of a transition-metal photosensitizer and a redox-active disulfide ligand directly coordinated to the metal center. A cyclometalated iridium-, as well as an organometallic rhenium photosensitizer decorated with a disulfide functionality on the bipyridyl ligand periphery, capable of storing two electrons and one proton, are presented. The photophysics of these complexes are investigated using a combination of (ultrafast) spectroscopy and non-adiabatic dynamics simulations, revealing a major influence of disulfide functionalization on the excited-state processes. Uptake of two electrons and one proton from the photo-excited state is achieved on the disulfide, forming a stable thiol-thiolate complex, and the underlying mechanism is investigated. Release of the stored redox equivalents can occur in the form of protons, H atoms, or formal hydride ions, as demonstrated by substrate reactivity and thermodynamic cycles. A comparatively low bond-dissociation free energy is found for the S−H bond of these complexes. This thesis sheds light on the use of disulfides as redox switch in molecular artificial photosynthetic systems and provides valuable insights into their photochemistry, as well as ground-state PCET chemistry.	de
dc.contributor.coReferee	Siewert, Inke Prof. Dr.
dc.contributor.thirdReferee	Schwarzer, Dirk Prof. Dr.
dc.contributor.thirdReferee	Wenger, Oliver Prof. Dr.
dc.contributor.thirdReferee	Krawczuk, Anna Prof. Dr.
dc.contributor.thirdReferee	Walker, Johannes C. L. Prof. Dr.
dc.subject.eng	photochemistry	de
dc.subject.eng	photophysics	de
dc.subject.eng	disulfide	de
dc.subject.eng	PCET	de
dc.subject.eng	hydrogen atom transfer	de
dc.subject.eng	hydride transfer	de
dc.subject.eng	redox-active ligand	de
dc.subject.eng	artificial photosynthesis	de
dc.subject.eng	photosensitizer	de
dc.identifier.urn	urn:nbn:de:gbv:7-ediss-15186-5
dc.date.embargoed	2025-02-28
dc.affiliation.institute	Fakultät für Chemie	de
dc.subject.gokfull	Chemie (PPN62138352X)	de
dc.description.embargoed	2025-02-28	de
dc.identifier.ppn	1884546242
dc.notes.confirmationsent	Confirmation sent 2024-03-27T13:45:01	de

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