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Time-Resolved Spectroscopy and Electronic Structure of Mono-and Dinuclear Pyridyl-Triazole/DPEPhos-Based Cu(I) Complexes

Grupe, M.; Boden, P.; Di Martino-Fumo, P.; Gui, X. 1; Bruschi, C. 2; Israil, R.; Schmitt, M.; Nieger, M.; Gerhards, M.; Klopper, W. ORCID iD icon 1; Riehn, C.; Bizzarri, C. 2; Diller, R.
1 Institut für Physikalische Chemie (IPC), Karlsruher Institut für Technologie (KIT)
2 Institut für Organische Chemie (IOC), Karlsruher Institut für Technologie (KIT)


The comprehensive results on two mononuclear pyridyl-triazole/DPEPhos based Cu(I) complexes and its extension to their two dinuclear analogues paves the road to addressing the complex coupling of the respective monomeric units, involving various physical and chemical properties as charge, (electronic) structure and (long-lived) excited state properties, relevant for applications.
Chemical and spectroscopic characterization of the mononuclear photosensitizers [(DPEPhos)Cu(I)(MPyrT)]$^{0/+}$ (CuL, CuLH) and their dinuclear analogues (Cu$_{2}$L’, Cu$_{2}$L'H$_{2}$), backed by (TD)DFT and high-level GW-Bethe-Salpeter equation calculations, exemplifies the complex influence of charge, nuclearity and structural flexibility on UV-induced photophysical pathways. Ultrafast transient absorption and step-scan FTIR spectroscopy reveal flattening distortion in the triplet state of CuLH as controlled by charge, which also appears to have a large impact on the symmetry of the long-lived triplet states in Cu$_{2}$L’ and Cu$_{2}$L'H$_{2}$. Time-resolved luminescence spectroscopy (solid state), supported by transient photodissociation spectroscopy (gas phase), confirm a lifetime of some tens of μs for the respective triplet states, as well as the energetics of thermally activated delayed luminescence, both being essential parameters for application of these materials based on earth-abundant copper in photocatalysis and luminescent devices.

Verlagsausgabe §
DOI: 10.5445/IR/1000139378
Veröffentlicht am 29.10.2021
DOI: 10.1002/chem.202102760
Zitationen: 7
Web of Science
Zitationen: 8
Zitationen: 11
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Organische Chemie (IOC)
Institut für Physikalische Chemie (IPC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 02.11.2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000139378
Erschienen in Chemistry - A European Journal
Verlag John Wiley and Sons
Band 27
Heft 61
Seiten 15252-15271
Vorab online veröffentlicht am 22.09.2021
Nachgewiesen in Web of Science
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