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Sterically encumbering m-terphenyl isocyanides are a class of metal-binding group that foster low-coordinate metal-center environments in coordination chemistry by exerting considerable intermolecular steric pressures between neighboring ligands. In the context of metal surfaces, the encumbering steric properties of the m-terphenyl isocyanides are shown to weaken the interaction between the metal-binding group and a planar substrate, leading to a preference for molecular adsorption at sites with convex curvature, such as the step edges and herringbone elbow sites on Au(111). Here, we investigate the site-selective binding of individual m-terphenyl isocyanide ligands on a Au(111) surface through scanning tunneling microscopy (STM) and inelastic electron tunneling spectroscopy (IETS). The site-dependent steric pressure alters the vibrational fingerprint of the m-terphenyl isocyanides, which is characterized with single-molecule precision through joint experimental and theoretical approaches. This study for the first time provides molecular-level insights into the steric-pressure-enabled surface binding selectivity as well as its effect on the chemical properties of individual m-terphenyl isocyanide ligands, thereby highlighting the potential to control the physical and chemical properties of metal surfaces through tailored ligand design.

Charge transport processes at interfaces which are governed by complex interfacial electronic structure play a crucial role in catalytic reactions, energy storage, photovoltaics, and many biological processes. Here, the first soft X-ray second harmonic generation (SXR-SHG) interfacial spectrum of a buried interface (boron/Parylene-N) is reported. SXR-SHG shows distinct spectral features that are not observed in X-ray absorption spectra, demonstrating its extraordinary interfacial sensitivity. Comparison to electronic structure calculations indicates a boron-organic separation distance of 1.9 {\AA}, wherein changes as small as 0.1 {\AA} result in easily detectable SXR-SHG spectral shifts (ca. 100s of meV). As SXR-SHG is inherently ultrafast and sensitive to individual atomic layers, it creates the possibility to study a variety of interfacial processes, e.g. catalysis, with ultrafast time resolution and bond specificity.

Charge transport processes at interfaces which are governed by complex interfacial electronic structure play a crucial role in catalytic reactions, energy storage, photovoltaics, and many biological processes. Here, the first soft X-ray second harmonic generation (SXR-SHG) interfacial spectrum of a buried interface (boron/Parylene-N) is reported. SXR-SHG shows distinct spectral features that are not observed in X-ray absorption spectra, demonstrating its extraordinary interfacial sensitivity. Comparison to electronic structure calculations indicates a boron-organic separation distance of 1.9 ��, wherein changes as small as 0.1 �� result in easily detectable SXR-SHG spectral shifts (ca. 100s of meV). As SXR-SHG is inherently ultrafast and sensitive to individual atomic layers, it creates the possibility to study a variety of interfacial processes, e.g. catalysis, with ultrafast time resolution and bond specificity., 19 pages