Lecourt, Constance and Melero, Raquel Utrera and Schiller, Jana and Moutier, Florent and Dorcet, Vincent and Calvez, Guillaume and Poidevin, Corentin and Costuas, Karine and Scheer, Manfred and Lescop, Christophe (2023) Phase dependence and mechanical and thermal ductility of the luminescence properties of tetranuclear Cu(<sc>i</sc>) metallacycle assemblies stabilized by ditopic organo-pnictogen (P,As) ligands. INORGANIC CHEMISTRY FRONTIERS, 10 (23). pp. 6976-6989. ISSN 2052-1553,
Full text not available from this repository. (Request a copy)Abstract
A new highly solid-state luminescent dicationic Cu(i)(4) metallacycle A based on a mixed P,As ligand assembly is reported for the first time. Surprisingly, as compared to a previously described related Cu(i)4 metallacycle B based on a similar P,P ligand, a moderate effect of the presence of arsenic atoms in the photophysical processes is observed. A thorough combined experimental and theoretical study is conducted revealing that, in Cu(i) polymetallic assemblies bearing pnictogen ligands, the substitution of a phosphorus atom by an arsenic atom does not cause systematically an alteration of the SOC values and therefore an improvement of the radiative relaxation rates. Intermolecular constraints applied on the gross molecular backbones can play a major role, inducing subtle but noticeable structural alteration impacting optical changes that may differentiate the photophysics of the assemblies regarding the pnictogen atom present. In line with this point, luminescence thermochromism and mechanochromism are observed and analyzed for both A and B assemblies, which moreover also display in the solid state at high temperature an original irreversible thermal crystalline transition that impacts photophysical properties. All in all, this study highlights the subtle and competitive effects that can rule out the photophysics of Cu(i) polymetallic assemblies based on organo-pnictogen ligands and reveals their stimuli-sensitive behaviours, allowing the facile preparation of different phases bearing contrast efficient luminescence properties.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ACTIVATED DELAYED FLUORESCENCE; AGGREGATION-INDUCED EMISSION; COPPER(I) COMPLEXES; MECHANOCHROMIC LUMINESCENCE; CUPROPHILIC INTERACTIONS; PHOTOPHYSICAL PROPERTIES; ROOM-TEMPERATURE; CU(I) COMPLEXES; SOLID-STATE; PHOSPHORESCENCE; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 22 Apr 2024 09:39 |
| Last Modified: | 22 Apr 2024 09:39 |
| URI: | https://pred.uni-regensburg.de/id/eprint/61857 |
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