Time-Resolved Spectroscopy and Electronic Structure of Mono-and Dinuclear Pyridyl-Triazole/DPEPhos-Based Cu(I) Complexes.
Merten GrupePit BodenPatrick Di Martino-FumoXin GuiCecilia BruschiRoumany IsrailMarcel SchmittMartin NiegerMarkus GerhardsWillem KlopperChristoph RiehnClaudia BizzarriRolf DillerPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2021)
Chemical and spectroscopic characterization of the mononuclear photosensitizers [(DPEPhos)Cu(I)(MPyrT)]0/+ (CuL, CuLH) and their dinuclear analogues (Cu2 L', Cu2 L'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 Cu2 L' and Cu2 L'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.
Keyphrases
- solid state
- energy transfer
- aqueous solution
- metal organic framework
- high resolution
- single molecule
- quantum dots
- molecular docking
- computed tomography
- density functional theory
- photodynamic therapy
- oxidative stress
- single cell
- diabetic rats
- sensitive detection
- genome wide
- subarachnoid hemorrhage
- drug induced
- gene expression
- solar cells
- peripheral blood