Phosphorescence enhancement by close metal–metal interaction in T1 excited state in a dinuclear copper(i) complex

The dinuclear copper(i) complex [Cu2(μ-dppm)2(lact)(μ-lact)] (1) (dppm = bis(diphenylphosphino)methane; lact = l-(+)-lactate) was synthesized and fully characterized both in solution and solid state. Variable temperature NMR experiments (1H and 31P), conductivity measurements and infrared spectrosco...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2019, Vol.48 (25), p.9276-9283
Main Authors: Bassoli, Simona, Ardizzoia, G Attilio, Therrien, Bruno, Brenna, Stefano
Format: Article
Language:English
Subjects:
Acetone
Coordination compounds
Copper
Copper compounds
Crystal structure
Crystallography
Density functional theory
Excitation
Mathematical analysis
Molecular orbitals
NMR
Nuclear magnetic resonance
Phosphorescence
Solid state
Spectrum analysis
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Summary:The dinuclear copper(i) complex [Cu2(μ-dppm)2(lact)(μ-lact)] (1) (dppm = bis(diphenylphosphino)methane; lact = l-(+)-lactate) was synthesized and fully characterized both in solution and solid state. Variable temperature NMR experiments (1H and 31P), conductivity measurements and infrared spectroscopy, suggest the occurrence of a fluxional behavior in solution involving the lactate anion. The crystal structure shows the presence of both monodentate and bridged lactate in the complex. In the solid state, 1 shows green phosphorescent emission characterized by a very large Stokes shift (161 nm, 1.09 eV) and a good absolute quantum yield (0.43). Calculations performed at the Density Functional Theory level demonstrate that the electronic transition responsible for the emission originates from a triplet excited state where the shortening of the Cu⋯Cu distance plays a crucial role.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt01565e