Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit Coupling

The electronic and structural alterations induced by the functionalization of the 1,10-phenanthroline (phen) ligand in [Cu(I) (phen-R2)2]+ complexes (R=H, CH3, tertio-butyl, alkyl-linkers) and their consequences on the luminescence properties and thermally activated delay fluorescence (TADF) activit...

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Veröffentlicht in:Materials Jg. 15; H. 15; S. 5222
Hauptverfasser: Gourlaouen, Christophe, Daniel, Chantal
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Basel MDPI AG 28.07.2022
MDPI
Schlagworte:
Approximation
Broken symmetry
Chemical Sciences
Copper
Coupling (molecular)
Density functional theory
Electron spin
Flattening
Ligands
Luminescence
Optical properties
Oscillator strengths
Photoluminescence
Spin-orbit interactions
Steric hindrance
Symmetry
ISSN:1996-1944, 1996-1944
Online-Zugang:Volltext
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Zusammenfassung:The electronic and structural alterations induced by the functionalization of the 1,10-phenanthroline (phen) ligand in [Cu(I) (phen-R2)2]+ complexes (R=H, CH3, tertio-butyl, alkyl-linkers) and their consequences on the luminescence properties and thermally activated delay fluorescence (TADF) activity are investigated using the density functional theory (DFT) and its time-dependent (TD) extension. It is shown that highly symmetric molecules with several potentially emissive nearly-degenerate conformers are not promising because of low S1/S0 oscillator strengths together with limited or no S1/T1 spin–orbit coupling (SOC). Furthermore, steric hindrance, which prevents the flattening of the complex upon irradiation, is a factor of instability. Alternatively, linking the phenanthroline ligands offers the possibility to block the flattening while maintaining remarkable photophysical properties. We propose here two promising complexes, with appropriate symmetry and enough rigidity to warrant stability in standard solvents. This original study paves the way for the supramolecular design of new emissive devices.
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ISSN:1996-1944
1996-1944
DOI:10.3390/ma15155222