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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
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Controlling Redox and Photophysical Properties of First-Row Transition Metal Complexes via Ligand Perhalogenation
Tim-Niclas Streit1, Malte Sellin2, Bruno Lazarevski2
1Freie Universität Berlin, Institut für Chemie und Biochemie, Fabeckstraße 34-36, 14195 Berlin, Germany.
Inorganic Chemistry
|February 28, 2026
Summary
Researchers synthesized nickel(0) complexes with perhalogenated ligands, finding they enhance π-acceptor strength and control redox potentials without changing excitation energies. This advances the design of nickel-based photoredox catalysts and photoactive materials.
Area of Science:
- Coordination Chemistry
- Organometallic Chemistry
- Photochemistry
Background:
- Ligand halogenation significantly impacts transition-metal complex properties.
- Fully halogenated ligand systems are underexplored.
- Controlling redox and photophysical properties is crucial for catalyst design.
Purpose of the Study:
- Synthesize and characterize homoleptic Ni(0) complexes with perhalogenated aryl isocyanide ligands.
- Investigate the effect of perhalogenation on electrochemical and photophysical properties.
- Explore the potential of these complexes in photoredox catalysis and material applications.
Main Methods:
- Synthesis and structural characterization of [Ni(CN-C6X5)4] (X = F, Cl) complexes.
- Comparative electrochemical studies (cyclic voltammetry).
- UV-Vis absorption spectroscopy and DFT calculations.
- Ultrafast transient absorption spectroscopy.
Main Results:
- Perfluorinated complexes show a significant anodic shift in the Ni(0)/Ni(I) couple (+0.03 V vs Fc+/0) due to enhanced π-acceptor strength.
- Metal-to-ligand charge-transfer (MLCT) energies were largely unchanged in perfluorinated species, attributed to concurrent HOMO/LUMO stabilization.
- Perchlorinated complexes exhibited red-shifted MLCT bands.
- 3MLCT excited states with lifetimes of 66-141 ps were observed.
Conclusions:
- Perhalogenated isocyanides are effective ligands for tuning excited-state redox potentials while maintaining excitation energies.
- Ligand perhalogenation is a viable strategy for designing robust Ni-based photoredox catalysts.
- Potential applications include luminescent devices, photocatalysis, and photodynamic therapy.
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