Results
Title

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

Authors

Grupe, Merten; Boden, Pit; Di Martino‐Fumo, Patrick; Gui, Xin; Bruschi, Cecilia; Israil, Roumany; Schmitt, Marcel; Nieger, Martin; Gerhards, Markus; Klopper, Wim; Riehn, Christoph; Bizzarri, Claudia; Diller, Rolf

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.

Subjects

TIME-resolved spectroscopy; LUMINESCENCE spectroscopy; ELECTRONIC structure; DELAYED fluorescence; FOURIER transform infrared spectroscopy; PHOTOSENSITIZERS; PHOTODISSOCIATION

Publication

Chemistry - A European Journal, 2021, Vol 27, Issue 61, p15251

ISSN

0947-6539

Publication type

Academic Journal

DOI

10.1002/chem.202102760