Making and breaking of chemical bonds in single nanoconfined molecules

Abstract

Nanoconfinement of catalytically active molecules is a powerful strategy to control their chemical activity; however, the atomic-scale mechanisms are challenging to identify. In the present study, the site-specific reactivity of a model rhenium catalyst is studied on the subnanometer scale for complexes confined within quasi–one-dimensional molecular chains on the Ag(001) surface by scanning tunneling microscopy. Injection of tunneling electrons causes ligand dissociation in single molecules. Unexpectedly, while half of the complexes show only the dissociation, the confined molecules show also the reverse reaction. On the basis of density functional theory calculations, this drastic difference can be attributed to the limited space in confinement. That is, the split-off ligand adsorbs closer to the molecule and the dissociation causes less structural disruption. Both of these facilitate the reverse reaction. We demonstrate formation and disruption of single chemical bonds of nanoconfined molecules with potential application in molecular data storage.

Testing functional anchor groups for the efficient immobilization of molecular catalysts on silver surfaces

“…1a are oriented along [110]. Nucleation of molecular monolayers is found to take place at well-oriented and covered step edges, and the layers show intrinsic long-range order of certain complexity 24 . Figure 1b shows a silver surface decorated by the sulfurated complex Rebpy S-S .…”

C−C Coupling in CO2 Electroreduction on Single Cu‐Modified Covalent Triazine Frameworks: A Static and Dynamic Density Functional Theory Study

“…The intermediate steps were created 7 images to be interpolated between the initial and final configurations. The manner of the relaxation of each geometries were based on a previous paper by Wenderoth et al [36] An artificial spring force constant was 5 eV/ Å 2 along the reaction tangents. The final force convergence accuracy on each atom was reduced to < 0.01 eV/Å.…”

Charge Recognition in Ru(bpy)32+ on a Metal Surface via Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy

“…59 Despite this exciting prospect, however, surface visualization and characterization of these types of dye molecules are rare. 60 The prototypical molecule, tris(2,2′bipyridine)ruthenium(II) (termed Ru(bpy) 3 2+ , Figure 1), consists of a central ruthenium core (in +2 oxidation state) with three bipyridine (bpy) functional groups in the octahedrally coordinated geometry (D 3 symmetry). The primary electronic absorption in the UV−visible spectrum at around 452 nm is controlled by the central Ru(II) core through a metal-to-ligand charge transfer (MLCT) transition.…”