title: Voltammetry and in situ scanning tunnelling spectroscopy of osmium, iron, and ruthenium complexes of 2,2':6',2''-terpyridine covalently linked to Au(111)-electrodes.
abstract: We have studied self-assembled molecular monolayers (SAMs) of complexes between Os(II)/(III), Fe(II)/(III), and Ru(II)/(III) and a 2,2',6',2''-terpyridine (terpy) derivative linked to Au(111)-electrode surfaces via a 6-acetylthiohexyloxy substituent at the 4'-position of terpy. The complexes were prepared in situ by first linking the terpy ligand to the surface via the S-atom, followed by addition of suitable metal compounds. The metal-terpy SAMs were studied by cyclic voltammetry (CV), and in situ scanning tunnelling microscopy with full electrochemical potential control of substrate and tip (in situ STM). Sharp CV peaks were observed for the Os- and Fe complexes, with interfacial electrochemical electron transfer rate constants of 6-50 s(-1). Well-defined but significantly broader peaks (up to 300 mV) were observed for the Ru-complex. Addition of 2,2'-bipyridine (bipy) towards completion of the metal coordination spheres induced voltammetric sharpening. In situ STM images of single molecular scale strong structural features were observed for the osmium and iron complexes. As expected from the voltammetric patterns, the surface coverage was by far the highest for the Ru-complex which was therefore selected for scanning tunnelling spectroscopy. These correlations displayed a strong peak around the equilibrium potential with systematic shifts with increasing bias voltage, as expected for a sequential two-step in situ ET mechanism.
authors.affiliation: Department of Chemistry, Technical University of Denmark, Building 207, DK-2800 Kongens Lyngby, Denmark.
authors.forename: Princia
authors.initials: P
authors.lastname: Salvatore
authors.forename: Allan Glargaard
authors.initials: AG
authors.lastname: Hansen
authors.forename: Kasper
authors.initials: K
authors.lastname: Moth-Poulsen
authors.forename: Thomas
authors.initials: T
authors.lastname: Bjørnholm
authors.forename: Richard John
authors.initials: RJ
authors.lastname: Nichols
authors.forename: Jens
authors.initials: J
authors.lastname: Ulstrup
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D004563:Electrochemistry; D004566:Electrodes; D006046:Gold / Q000737:chemistry*; D007501:Iron / Q000737:chemistry; D016252:Microscopy, Scanning Tunneling; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009992:Osmium / Q000737:chemistry; D010316:Particle Size; D011725:Pyridines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry; D013499:Surface Properties
chemical_list: C517923:(2,2'-6',2'')-terpyridine; D056831:Coordination Complexes; D009944:Organoplatinum Compounds; D011725:Pyridines; D009992:Osmium; D006046:Gold; D012428:Ruthenium; D007501:Iron