|
|||||
|
|
Time-Resolved Spectroscopy and Electronic Structure of Mono-and Dinuclear Pyridyl-Triazole/DPEPhos-Based Cu(I) Complexes |
|
| Authors: | Dr Merten Grupe Pit Boden Patrick Di Martino-Fumo Dr Xin Gui Cecilia Bruschi Roumany Israil Marcel Schmitt Dr Martin Nieger Prof Dr Markus Gerhards Prof Dr Wim Klopper Dr Christoph Riehn Dr Claudia Bizzarri Prof Dr Rolf Diller |
| Institution: | 1. Department of Physics, TU Kaiserslautern, Erwin-Schrödinger-Straße 46, 67663 Kaiserslautern, Germany
These authors contributed equally to this work.;2. Department of Chemistry, TU Kaiserslautern, Erwin-Schrödinger-Straße 52, 67663 Kaiserslautern, Germany These authors contributed equally to this work.;3. Department of Chemistry, TU Kaiserslautern, Erwin-Schrödinger-Straße 52, 67663 Kaiserslautern, Germany;4. Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe, Germany;5. Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany;6. Department of Chemistry, University of Helsinki, A.I. Virtasen aukio 1, 00014 Helsinki, Finland;7. Department of Chemistry, TU Kaiserslautern, Erwin-Schrödinger-Straße 52, 67663 Kaiserslautern, Germany Research Center OPTIMAS, Erwin-Schrödinger-Straße 46, 67663 Kaiserslautern, Germany Deceased December 28th 2020;8. Department of Physics, TU Kaiserslautern, Erwin-Schrödinger-Straße 46, 67663 Kaiserslautern, Germany |
| Abstract: | Chemical and spectroscopic characterization of the mononuclear photosensitizers (DPEPhos)Cu(I)(MPyrT)]0/+ ( CuL , CuLH ) and their dinuclear analogues ( Cu2L’ , Cu2L'H2 ), 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 Cu2L’ and Cu2L'H2 . 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. |
| Keywords: | copper(I) complexes cooperative effects flattening distortion photosensitizers time-resolved spectroscopy |