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-R<sub>2</sub>)<sub>2</sub>]<sup>+</sup> complexes (R=H, CH<sub>3</sub>, <i>tertio</i>-butyl, alkyl-linkers)...
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| Language: | English |
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MDPI AG
2022-07-01
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| Series: | Materials |
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| Online Access: | https://www.mdpi.com/1996-1944/15/15/5222 |
| _version_ | 1797413339359346688 |
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| author | Christophe Gourlaouen Chantal Daniel |
| author_facet | Christophe Gourlaouen Chantal Daniel |
| author_sort | Christophe Gourlaouen |
| collection | DOAJ |
| description | The electronic and structural alterations induced by the functionalization of the 1,10-phenanthroline (phen) ligand in [Cu(I) (phen-R<sub>2</sub>)<sub>2</sub>]<sup>+</sup> complexes (R=H, CH<sub>3</sub>, <i>tertio</i>-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 S<sub>1</sub>/S<sub>0</sub> oscillator strengths together with limited or no S<sub>1</sub>/T<sub>1</sub> 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. |
| first_indexed | 2024-03-09T05:16:14Z |
| format | Article |
| id | doaj.art-af63c347799e47dfb43a86d8ee161f11 |
| institution | Directory Open Access Journal |
| issn | 1996-1944 |
| language | English |
| last_indexed | 2024-03-09T05:16:14Z |
| publishDate | 2022-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Materials |
| spelling | doaj.art-af63c347799e47dfb43a86d8ee161f112023-12-03T12:45:23ZengMDPI AGMaterials1996-19442022-07-011515522210.3390/ma15155222Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit CouplingChristophe Gourlaouen0Chantal Daniel1Laboratoire de Chimie Quantique Institut de Chimie UMR 7177, CNRS, Université de Strasbourg, 4, Rue Blaise Pascal CS 90032, F-67081 Strasbourg, FranceLaboratoire de Chimie Quantique Institut de Chimie UMR 7177, CNRS, Université de Strasbourg, 4, Rue Blaise Pascal CS 90032, F-67081 Strasbourg, FranceThe electronic and structural alterations induced by the functionalization of the 1,10-phenanthroline (phen) ligand in [Cu(I) (phen-R<sub>2</sub>)<sub>2</sub>]<sup>+</sup> complexes (R=H, CH<sub>3</sub>, <i>tertio</i>-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 S<sub>1</sub>/S<sub>0</sub> oscillator strengths together with limited or no S<sub>1</sub>/T<sub>1</sub> 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.https://www.mdpi.com/1996-1944/15/15/5222luminescenceTADFcopper(I) phenanthroline functionalizationdensity functional theorynuclear relaxationsymmetry-breaking spin–orbit coupling |
| spellingShingle | Christophe Gourlaouen Chantal Daniel Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit Coupling Materials luminescence TADF copper(I) phenanthroline functionalization density functional theory nuclear relaxation symmetry-breaking spin–orbit coupling |
| title | Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit Coupling |
| title_full | Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit Coupling |
| title_fullStr | Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit Coupling |
| title_full_unstemmed | Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit Coupling |
| title_short | Towards Optimized Photoluminescent Copper(I) Phenanthroline-Functionalized Complexes: Control of the Photophysics by Symmetry-Breaking and Spin–Orbit Coupling |
| title_sort | towards optimized photoluminescent copper i phenanthroline functionalized complexes control of the photophysics by symmetry breaking and spin orbit coupling |
| topic | luminescence TADF copper(I) phenanthroline functionalization density functional theory nuclear relaxation symmetry-breaking spin–orbit coupling |
| url | https://www.mdpi.com/1996-1944/15/15/5222 |
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