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Stabilization of Luminescent Mononuclear Three-Coordinate CuI Complexes by Two Distinct Cavity-Shaped Diphosphanes
Tuan-Anh Phan1,2, Matthieu Jouffroy3, Dominique Matt3
1Équipe Confinement Moléculaire et Catalyse, Institut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, CS90032, 67081, Strasbourg cedex, France.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|November 24, 2023
Summary
Two novel diphosphine ligands derived from cyclodextrins create unique copper(I) complexes. These complexes exhibit distinct luminescence properties due to the ligand
Area of Science:
- Organometallic Chemistry
- Supramolecular Chemistry
- Photophysics
Background:
- Cyclodextrins (CDs) are widely used in host-guest chemistry.
- Phosphine ligands play a crucial role in coordination chemistry.
- Copper(I) complexes are known for their luminescent properties.
Purpose of the Study:
- To synthesize novel cavity-shaped diphosphine ligands using cyclodextrin derivatives.
- To explore the coordination chemistry of these ligands with copper(I) halides.
- To investigate the photophysical properties of the resulting mononuclear copper(I) complexes.
Main Methods:
- Synthesis of diphenyl(2-phosphanylphenyl)phosphane and an α-cyclodextrin-derived dimesylate.
- Formation of mononuclear [CuX(PP)] complexes (X=Cl, Br, I).
- Characterization using spectroscopic techniques (absorption, emission) and lifetime measurements.
Main Results:
- Two distinct cavity-shaped cis-chelating diphosphanes were synthesized.
- Mononuclear copper(I) complexes were formed, with the metal ion confined within the CD cavity.
- The Cu(I) complexes displayed significantly different luminescence properties and longer excited-state lifetimes compared to cavity-free analogues.
- Evidence suggests close-lying charge-transfer (MLCT, XLCT) and triplet ligand-centered (LC) excited states.
Conclusions:
- The synthesized cyclodextrin-derived diphosphines effectively confine copper(I) ions.
- The steric and electronic environment of the CD cavity profoundly influences the luminescence of the copper(I) complexes.
- These findings offer insights into the design of novel luminescent coordination compounds with tailored properties.
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