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@article{19991b1e3e944189a2e3a56b789ceec9,
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",
publisher = "Royal Society of Chemistry",
author = "Princia Salvatore and Hansen, {Allan Glargaard} and Kasper Moth-Poulsen and Thomas Bjørnholm and Nichols, {Richard John} and Jens Ulstrup",
year = "2011",
doi = "10.1039/c1cp21197h",
volume = "13",
number = "32",
pages = "14394--14403",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",

}

RIS

TY - JOUR

T1 - 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

A1 - Salvatore,Princia

A1 - Hansen,Allan Glargaard

A1 - Moth-Poulsen,Kasper

A1 - Bjørnholm,Thomas

A1 - Nichols,Richard John

A1 - Ulstrup,Jens

AU - Salvatore,Princia

AU - Hansen,Allan Glargaard

AU - Moth-Poulsen,Kasper

AU - Bjørnholm,Thomas

AU - Nichols,Richard John

AU - Ulstrup,Jens

PB - Royal Society of Chemistry

PY - 2011

Y1 - 2011

N2 - 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.

AB - 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.

U2 - 10.1039/c1cp21197h

DO - 10.1039/c1cp21197h

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 32

VL - 13

SP - 14394

EP - 14403

ER -