Experimental and theoretical study of the adsorption of fumaramide [2]rotaxane on Au(111) and Ag(111) surfaces

Abstract

Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Mendoza, S. M., Whelan, C. M., Jalkanen, J-P., Zerbetto, F., Gatti, F., Kay, E. R., ... Rudolf, P. (2005 Thin films of fumaramide ͓2͔rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a "bead and thread" configuration, were prepared by vapor deposition on both Ag͑111͒ and Au͑111͒ substrates. X-ray photoelectron spectroscopy ͑XPS͒ and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide ͓2͔rotaxane adsorption on Au͑111͒, the presence of certain out-of-plane phenyl ring and Au-O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide ͓2͔rotaxane and the Ag͑111͒ or Au͑111͒ surface.

Molecular Architectonic on Metal Surfaces

“…In special cases even reversible conformational switching phenomena become apparent (53). Characterizing the adsorption configuration of molecules with multiple internal degrees of freedom is a real challenge (54,55). Furthermore, the symmetry reduction associated with the 2D confinement brings along a rich variety of chirality phenomena, which have been reviewed at length elsewhere (27,56).…”

Theoretical Study on Conformation Dynamics of Three-Station Molecular Shuttle in Different Environments and its Influence on NMR Chemical Shifts and Binding Interactions

“…With an emphasis on the solvent-dependent conformational flexibility, Naresh K. Jena et al performed a MD study on the diketopyrrolopyrrole-based [2]rotaxane in the TIP3P water environment or in chloroform and DMSO solvents (which were treated by an amber force field) . MD simulations were also successfully adopted in visualizing the behavior and configuration of the absorbed fumaramide [2]rotaxane film on Ag(111) and Au(111) substrates …”

“…37 MD simulations were also successfully adopted in visualizing the behavior and configuration of the absorbed fumaramide [2]rotaxane film on Ag(111) and Au(111) substrates. 38 Until now, most theoretical simulations were focused on dual station [2]rotaxanes with two switchable binding sites (stations) on thread, although several tristable molecular shuttles were recently created with three different stations. 39−45 The existence of three binding units on the long thread adds the complexity of the subtle noncovalent interactions between the macrocycle and the different stations, especially when the explicit solvent molecules are involved.…”

Charge Transfer and Chemisorption of Fullerene Molecules on Metal Surfaces: Application to Dynamics of Nanocars

“…Despite the limitations of the Qeq method, it has been used in combination with other molecular mechanics methods for the number of adsorbates on various metal surfaces, ,, including C 60 on gold. , However, the predicted amount of charge, transferred from the metal to fullerene, calculated with such approaches is smaller than observed experimentally …”