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

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.