A quantum chemical study of substituent effects on CN bonds in aryl isocyanide molecules adsorbed on the Pt surface

Abstract

A periodicity implemented scheme of NBO theory and normal mode analysis has been employed to investigate the chemical bond strength tendency for aryl isocyanide molecules with different para-substituted groups adsorbed on the Pt(111) surface.

Correlating the orbital overlap area and vibrational frequency shift of an isocyanide moiety adsorbed on Pt and Pd covered Au(111) surfaces

“…30,56 Table S8 (ESI†) shows that the ν CN frequency of the PIC molecule adsorbed on the top site of the metal surface is blue shifted compared to that of the free molecule, consistent with previous studies. 13,30,32,57 We note that the tendency of the ν CN frequency shift is the same as the result obtained in the cluster model. However, the amount of ν CN frequency shift of PIC adsorption on the top site of single crystal surfaces is higher than that of the cluster structure.…”

“…55 And the orbital overlap population analysis, adiabatic energy decomposition analysis, and the periodicity natural bond orbital method have been successfully used to discuss the properties of the chemical bonds of CRN and CRO and their interaction with the metal surface. [56][57][58][59] Despite the significant advances, establishing a clear correlation between the vibrational frequency shift of adsorbed molecules and the electronic structure of the metal surface and the orbital interaction between molecules and the metal surface remains ambiguous.…”

Identifying Substrate-Dependent Chemical Bonding Nature at Molecule/Metal Interfaces Using Vibrational Sum Frequency Generation Spectroscopy and Theoretical Calculations

“…45 We have investigated the NC bond strength of X−C 6 H 4 −NC molecules on a platinum surface using periodic-boundary density functional theory (DFT) calculations with periodic NBO analysis, concentrating on the substituent effect. 22 The "volcano-like" trend of isolated molecules was considerably changed for molecule adsorbed on the Pt surface when the NC stretching frequencies and bond order derived from NBO analysis were plotted as a function of Hammett constant 46,47 for substituent X. This study shows that NBO analysis of the chemical bonds of various organic molecules adsorbed on a surface can provide a deeper understanding of the interaction between molecules and the surface.…”

“…The H− C 6 H 4 −NC molecules perpendicularly adsorb on the metal surface, which is similar to our previous results. 22 The N−C bond lengths and metal−C interatomic distances are summarized in Table 1. The N−C bond lengths show the same value for three free molecules, while they become slightly shorter for the molecule adsorbed on Au and Ag surfaces.…”

Medicinal Chemistry of Isocyanides

“…As a confirmation, when electron withdrawing groups are present on the phenyl ring this property is enhanced. , When the back-donation prevails, the linearity with the metal is lost and such complexes display a dihedral angle of 130–140° between the metal and the isocyano ligand. In comparison, a standard metal methylisocyanide complex is linear with a dihedral angle of 180° .…”