Dokument: TADF in Copper(I) Complexes bearing an Anionic N-Heterocyclic Carbene
| Titel: | TADF in Copper(I) Complexes bearing an Anionic N-Heterocyclic Carbene | |||||||
| URL für Lesezeichen: | https://docserv.uni-duesseldorf.de/servlets/DocumentServlet?id=63675 | |||||||
| URN (NBN): | urn:nbn:de:hbz:061-20230919-104836-1 | |||||||
| Kollektion: | Dissertationen | |||||||
| Sprache: | Englisch | |||||||
| Dokumententyp: | Wissenschaftliche Abschlussarbeiten » Dissertation | |||||||
| Medientyp: | Text | |||||||
| Autor: | Schmeinck, Philipp [Autor] | |||||||
| Dateien: |
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| Beitragende: | Prof. Dr. Ganter, Christian [Gutachter] Jun.-Prof. Dr. Suta, Markus [Gutachter] | |||||||
| Stichwörter: | Metallorganische Chemie | |||||||
| Dewey Dezimal-Klassifikation: | 500 Naturwissenschaften und Mathematik » 540 Chemie | |||||||
| Beschreibung: | The present work investigates the coordination chemistry of an anionic diamido-NHC with copper(I) and explores the photophysical properties of such complexes with particular reference to possible TADF behaviour. Several heteroleptic linear and trigonal planar copper(I) complexes incorporating pnictogen- or chalcogen-based ligands such as pyridines, triphenylphosphine, and seleno ureas were synthesized. The synthetic route begins with a 1D coordination polymer, composed of the NHC and copper(I) ions in a linear coordination arrangement. Addition of ligands to suspensions of this polymer generates the respective monomeric target complexes. The synthesis and the identity of the complexes in solution is subject to an equilibrium between them and oligomeric material. Molecular structures of the pnictogen-based complexes obtained via SC-XRD reveal intermolecular contacts between the electron-rich carbene backbone and electron-deficient pyridine moieties in solid state. These contacts are attributed to the high dipole moments of the complexes. An in-depth photophysical analysis was conducted with four selected compounds. Due to the equilibrium in solution, spectroscopic methods are adapted to ensure defined and reproducible sample compositions. In solution, addition of excess ligand is needed to push the equilibrium towards the monomeric complexes, while measurements on solid-state samples were conducted both on neat powders and on their suspensions in liquid or solid cyclohexane, the latter allowing measurements in standard cuvettes. The obtained results from the suspensions align well with those from powdered samples. Steady-state and time-resolved spectroscopy techniques were employed to investigate excitation behaviour and confirm potential TADF properties. The emission spectra of the complexes range from blue (451 nm) to orange (591 nm), covering a significant portion of the visible light spectrum. Time-resolved spectroscopy reveals a highly diverse emission behaviour, with one compound relaxing predominantly via the prompt fluorescence pathway and another via a long-lived phosphorescence. Temperature-dependent steady-state and time-resolved spectroscopy suggests delayed fluorescence for two complexes incorporating electron-poor pyridines, indicated by a spectral redshift and elongated lifetimes in the μs domain upon cooling. Excitation power dependant measurements indicate an emission kinetic of first order, excluding TTA as source of this emission. Time-resolved emission spectroscopy (TRES) provides a detailed insight into the types of emission involved from early nanoseconds to
late milliseconds and from 270 K down to 10 K. It provides a comprehensive overview of the processes involved and sheds light on the excited-state's intricate nature of the compounds analysed. | |||||||
| Lizenz: |  Dieses Werk ist lizenziert unter einer Creative Commons Namensnennung 4.0 International Lizenz | |||||||
| Bezug: | Institut für Anorganische Chemie I, Abteilung für Metallorganische Chemie, August 2019 bis August 2023 | |||||||
| Fachbereich / Einrichtung: | Mathematisch- Naturwissenschaftliche Fakultät » WE Chemie » Anorganische Chemie und Strukturchemie | |||||||
| Dokument erstellt am: | 19.09.2023 | |||||||
| Dateien geändert am: | 19.09.2023 | |||||||
| Promotionsantrag am: | 18.07.2023 | |||||||
| Datum der Promotion: | 22.08.2023 |
