Local excitation of confined molecule-surface hybrid systems

by Ole Bunjes
Doctoral thesis
Date of Examination:2022-06-15
Date of issue:2022-11-28
Advisor:PD Dr. Martin Wenderoth
Referee:PD Dr. Martin Wenderoth
Referee:Prof. Dr. Stefan Mathias
Referee:Prof. Dr. Vasily Moshnyaga
Referee:Prof. Dr. Claus Ropers
Referee:Prof. Dr. Cynthia A. Volkert
Referee:Prof. Dr. Alec M. Wodtke
Persistent Address: http://dx.doi.org/10.53846/goediss-9574

 

 

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Abstract

English

Molecule-surface hybrid systems promise solutions for a variety of technological challenges – including the development of efficient catalysts as well as of molecular electronic devices. In this work, different molecule surface hybrid systems have been introduced and thoroughly investigated. Therefore, two representatives of a famous class of molecular rhenium catalysts were successfully deposited onto clean Ag(001) surfaces. Upon deposition both complexes were shown to stay chemically intact. Their surface adsorption and their local electronic excitation were studied by a spectrum of spectroscopic techniques, scanning tunneling microscopy and density functional theory calculations. High-quality self-assembled molecular monolayers of fac Re(bpy)(CO)3Cl (bpy = 2,2’-bipyridine) were found to provide several functionalities essential for the realization of atomic scale memory. Hence, these systems are seen as promising candidates for studying molecular data storage – even under ambient conditions. Taking stock of the potential application in electrochemical CO2 reduction, the results on complexes of fac [Re(S−Sbpy)(CO)3Cl] (S−Sbpy = 3,3’-disulfide-2,2’-bipyridine) adsorbed to the silver surface are motivator for future investigations. Strategies for effective anchoring must be evaluated and, once successful, this will allow to quantitatively relate the adsorption configuration with the catalytic activity.
Keywords: CO2 reduction catalysis; rhenium bipyridine; surface anchoring; scanning tunneling microscopy; Ag(001); local electronic excitation; surface chemistry; molecular self-assembly