Electronic Coupling of Molecular Complexes to Au Electrodes Mediated via Host-Guest Interactions
Abstract
Immobilization of molecular catalysts onto electrode surfaces using host-guest (HG) interactions enables the facile regeneration of electrodes following catalyst degradation. Beyond this practical aspect, the architecture also offers a unique way to study the electronic coupling of molecules to the electrode through a nominally insulating linker. Here, we employ surface-enhanced infrared absorption spectroscopy (SEIRAS) to characterize the binding and electronic coupling of Au-bound HG complexes. Distinct spectral features and binding kinetics differentiate host-bound species from physisorbed analogues, confirming well-defined HG assemblies on the surface. Analysis of the wavenumber shifts of the guest as a function of applied potential suggests that while the coupling of physisorbed guests with the surface is not strong, the host-bound guests show a substantial electronic coupling considering their distance from the surface of similar to 1.3 nm. Density functional theory calculations reveal the key role of the host in mediating this long-range coupling between the Au surface and the guest.
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BibTeX
@article{tuncay2026electronic,
title = {{Electronic Coupling of Molecular Complexes to Au Electrodes Mediated via Host-Guest Interactions}},
author = {Isik Tuncay and Tzu-Chin Chang Chien and Florian Keller and Helena Roithmeyer and Laurent Severy and Olivier Blacque and Marcella Iannuzzi and Murielle F. Delley and S. David Tilley},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.5c12957},
url = {https://hal.science/hal-05527498v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Electronic Coupling of Molecular Complexes to Au Electrodes Mediated via Host-Guest Interactions
AU - Isik Tuncay
AU - Tzu-Chin Chang Chien
AU - Florian Keller
AU - Helena Roithmeyer
AU - Laurent Severy
AU - Olivier Blacque
AU - Marcella Iannuzzi
AU - Murielle F. Delley
AU - S. David Tilley
PY - 2026
DA - 2026/10/22
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.5c12957
UR - https://hal.science/hal-05527498v1
AB - Immobilization of molecular catalysts onto electrode surfaces using host-guest (HG) interactions enables the facile regeneration of electrodes following catalyst degradation. Beyond this practical aspect, the architecture also offers a unique way to study the electronic coupling of molecules to the electrode through a nominally insulating linker. Here, we employ surface-enhanced infrared absorption spectroscopy (SEIRAS) to characterize the binding and electronic coupling of Au-bound HG complexes. Distinct spectral features and binding kinetics differentiate host-bound species from physisorbed analogues, confirming well-defined HG assemblies on the surface. Analysis of the wavenumber shifts of the guest as a function of applied potential suggests that while the coupling of physisorbed guests with the surface is not strong, the host-bound guests show a substantial electronic coupling considering their distance from the surface of similar to 1.3 nm. Density functional theory calculations reveal the key role of the host in mediating this long-range coupling between the Au surface and the guest.
SN - 0002-7863
SN - 1520-5126
ER -