Solid state luminescence of phosphine-EWO ligands with fluorinated chalcone skeletons and their PdX2 complexes: metal-promoted phosphorescence enhancement

Complexes trans-[PdX2L2] (X = Cl and Br), where L is 1-(PR2),2-(CH=CH–C(O)Ph)-C6F4 (R = Ph, Cy, and iPr), display phosphorescent emission in the solid state, whereas due to their substantially lower lifetimes, the free ligands exhibit fluorescent behaviour. Alternatively, structurally identical deri...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2023-03, Vol.52 (11), p.3265-3269
Main Authors: Ponce-de-León, Jaime, Peñas-Defrutos, Marconi N, Vélez, Andrea, Aullón, Gabriel, Espinet, Pablo
Format: Article
Language:English
Subjects:
Fluorescence
Ligands
Luminescence
Molecular orbitals
Palladium
Phosphines
Phosphorescence
Solid state
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container_title Dalton transactions : an international journal of inorganic chemistry
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creator Ponce-de-León, Jaime
Peñas-Defrutos, Marconi N
Vélez, Andrea
Aullón, Gabriel
Espinet, Pablo
description Complexes trans-[PdX2L2] (X = Cl and Br), where L is 1-(PR2),2-(CH=CH–C(O)Ph)-C6F4 (R = Ph, Cy, and iPr), display phosphorescent emission in the solid state, whereas due to their substantially lower lifetimes, the free ligands exhibit fluorescent behaviour. Alternatively, structurally identical derivatives with halide replaced by CN− or Pd replaced by Pt are non-emissive. DFT calculations explain this diverse behaviour, showing that the hybridization of orbitals of the MX2 moiety with those of the chalcone fragment of ligands is significant only for the LUMO of the emissive compounds. In other words, in our complexes, only MLMCT processes (LM = Metal-perturbed Ligand-centered orbital) lead to observable luminescence.
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subjects Fluorescence
Ligands
Luminescence
Molecular orbitals
Palladium
Phosphines
Phosphorescence
Solid state
title Solid state luminescence of phosphine-EWO ligands with fluorinated chalcone skeletons and their PdX2 complexes: metal-promoted phosphorescence enhancement
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