Photochemistry and Ultrafast Dynamics of Mass-selected Multinuclear Coinage Metal Complexes Studied by Electronic Photodissociation Ion Spectroscopy in an Ion Trap
- Subject of this thesis is the investigation of photo-induced ultrafast elementary processes within the electronic excited-state manifold in mass-selected multinuclear coinage metal complexes (CMCs) in the gas phase. The chief objective is to ascertain how the intramolecular deactivation dynamics and gas phase reactivity are influenced by so-called metallophilic interactions between multiple d^10/d^8 metal centers, which in turn give rise to metal-delocalized electronic transitions. To this end, suitable molecular precursor ions were transferred into the gas phase by electrospray ionization (ESI) and subsequently isolated, activated, and finally analyzed in a Paul-type quadrupole ion trap (QIT) mass spectrometer. The QIT is modified to accept UV/Vis/NIR irradiation from a femtosecond laser setup. By combining several ion trap-based ion activation techniques and electronic photodissociation (PD) spectroscopy, the fragmentation pathways, as well as intrinsic optical properties (electronic PD spectra) of ionic CMCs are explored. In addition, the unconventional time-resolved transient photodissociation (t-PD) method, based on a femtosecond pump-probe excitation scheme, was employed for the first time on CMC ions in isolation, in order to elucidate their intrinsic photodynamics. This thesis mainly comprises five publications, covering the mass spectrometric and laser spectroscopic characterization of multinuclear Ag(I), Au(I), and Pt(II) based ionic complexes.
Author: | Sebastian KruppaORCiD |
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URN: | urn:nbn:de:hbz:386-kluedo-62586 |
DOI: | https://doi.org/10.26204/KLUEDO/6258 |
Advisor: | Christoph RiehnORCiD |
Document Type: | Doctoral Thesis |
Language of publication: | English |
Date of Publication (online): | 2021/02/11 |
Year of first Publication: | 2021 |
Publishing Institution: | Technische Universität Kaiserslautern |
Granting Institution: | Technische Universität Kaiserslautern |
Acceptance Date of the Thesis: | 2021/01/15 |
Date of the Publication (Server): | 2021/02/16 |
GND Keyword: | Ionenfalle; Photodissoziation; Münzmetall; Silberkomplexe; Femtosekundenspektroskopie |
Page Number: | 258 |
Faculties / Organisational entities: | Kaiserslautern - Fachbereich Chemie |
DDC-Cassification: | 5 Naturwissenschaften und Mathematik / 540 Chemie |
PACS-Classification (physics): | 30.00.00 ATOMIC AND MOLECULAR PHYSICS |
Licence (German): | Creative Commons 4.0 - Namensnennung, nicht kommerziell, keine Bearbeitung (CC BY-NC-ND 4.0) |