Theoretical exploration of the forces governing the interaction between gold–phthalocyanine and gold surface clusters

Abstract

Here we aim to explore the nature of the forces governing the adsorption of gold–phthalocyanine on gold substrates.

Closed-shell d10–d10 in [AuCl(CNR)]n and [AuCl(CO)]n (n = 1, 2; R = –H, –CH3, –Cy) complexes: quantum chemistry study of their electronic and optical properties

“…30,31 From a theoretical point of view, metallophilic interactions have been understood as being a contribution of two terms to the equilibrium distance: dispersion and ionic. [32][33][34][35][36][37][38][39][40][41][42][43][44] Relativistic effects contribute between 20% and 30% to the energy of interactions 14 for heavy atoms. In recent years, researchers have proposed that the nature of metallophilic interactions is represented by strong Pauli repulsion at close range, which is balanced with the dispersion and ionic contributions as the stabilizing parts of the interaction, [45][46][47] acting as a driving force for orbital interactions among the metallic centers.…”

Is there a Covalent Au(I)–Au(I) Bond in the trans-(AuX)2 (X = F, Cl, Br, I) Structure? A Post-Hartree–Fock and Density Functional Theory Study

“…As a reference, the van der Waals Au–Au distances from the crystal structure data obtained from complexes involving aurophilic interactions are between 280 and 350 pm . Meanwhile, based on reported theoretical models − focused on the study of the binding energies of aurophilic interactions, the Au–Au strength was within the range of 5–25 kcal/mol, a range in which the data here presented for the trans-(AuX) 2 models is located. This behavior could suggest the presence of a combination of physical forces that will cause the shortening of the Au–Au distance despite the low interaction energies.…”

“…This phenomenon is known as metallophilic interaction, and in the particular case that involves gold atoms, it is defined as “aurophilic interaction”. − These closed-shell interactions are estimated to be energetically similar to hydrogen bonds (7–17 kJ/mol) in the case of gold­(I), although these are weaker for silver­(I), copper­(I), platinum­(II), and other metals. − The metallophilic interaction has been determined experimentally via solid-state X-ray diffraction − and NMR/absorption/emission/Raman spectroscopic measurements . From a theoretical point of view, the metallophilic attraction has been understood as the contribution of two terms to the equilibrium distance: dispersion and ionic. − The relativistic effects contribute between 20 and 30% to the energy of interaction for heavy atoms like Pt, Au, Tl, Hg, Pb, and Bi.…”

“…This phenomenon is known as metallophilic interaction, and in the particular case that involves gold atoms, it is defined as “aurophilic interaction”. − These closed-shell interactions are estimated to be energetically similar to hydrogen bonds (7–17 kJ/mol) in the case of gold­(I), although these are weaker for silver­(I), copper­(I), platinum­(II), and other metals. − The metallophilic interaction has been determined experimentally via solid-state X-ray diffraction − and NMR/absorption/emission/Raman spectroscopic measurements . From a theoretical point of view, the metallophilic attraction has been understood as the contribution of two terms to the equilibrium distance: dispersion and ionic. − The relativistic effects contribute between 20 and 30% to the energy of interaction for heavy atoms like Pt, Au, Tl, Hg, Pb, and Bi. On the other hand, some groups such as Hoffmann and Alvarez, using extended Hückel calculations, proposed that the metallophilic interaction was due to hybridization between ( n – 1)­d and nsnp orbitals. − Also, in recent years, some researchers have proposed that the metallophilic interaction is driven by the balance between strong Pauli repulsion at a close range − and the orbital interaction among the metallic centers.…”

Closed-shell d10–d10 mechanochromic [AuPh(CNPh)]n complex: quantum chemistry electronic and optical properties

“…[31][32][33][34][35][36][37][38][39][40][41] These closed-shell interactions are estimated to be energetically similar to hydrogen bonds (7-20 kJ mol −1 ) in the case of gold(I). [42][43][44][45] The aurophilic interaction has been experimentally determined via solid-state X-ray diffraction [23][24][25][26] and NMR/ absorption/emission/Raman spectroscopic measurements. 27,28 From a theoretical point of view, gold interactions can be understood as the contribution of two terms to the equilibrium distance: dispersion and ionic interactions.…”