Molecular-Scale Insights into the Heterogeneous Interactions between an m-Terphenyl Isocyanide Ligand and Noble Metal
Liya Bi1,2, Yufei Wang2,3, Zhe Wang4,5
1Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0309, United States.
Abstract:
The structural and chemical properties of metal nanoparticles are often dictated by their interactions with molecular ligand shells. These interactions are highly material-specific and can vary significantly even among elements within the same group or materials with similar crystal structure. In this study, we surveyed the heterogeneous interactions between an m-terphenyl isocyanide ligand and Au and Ag nanoparticles (NPs) at the single-molecule limit. Specifically, we found that the ligation behavior with this molecule differs significantly between that of Au and AgNPs. Surface-enhanced Raman spectroscopy measurements revealed unique enhancement factors for two molecular vibrational modes between two metal surfaces, indicating different ligand binding geometries. Molecular-level characterization using scanning tunneling microscopy allowed us to directly visualize these variations between Ag and Au surfaces, which we assign as two distinct binding mechanisms. This molecular-scale visualization provides clear insights into the different ligand-metal interactions as well as the chemical behavior and spectroscopic characteristics of isocyanide-functionalized NPs.
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