On the influence of metal nanoparticle and π-system sizes in the stability of noncovalent adducts: a theoretical study

Herein we have computationally evaluated the relationship between Ag and Au nanoparticle (Ag/AuNP) size and π-surface extension in the formation of noncovalent complexes at the PBE0-D3/def2-TZVP level of theory. The NP-π interaction is known in supramolecular chemistry as a Regium-π bond (Rg-π), and differentiates from classical coordination bonds in strength and type of metal orbitals involved. In this study, the Rg-π complexes involved small Ag/AuNPs composed by 1 to 5 atoms and benzene, naphthalene and anthracene as π-systems, being characterized using several molecular modeling tools, including molecular electrostatic potential (MEP) calculations, energy decomposition analysis (EDA), quantum theory of atoms in molecules (QTAIM), non covalent interaction plot (NCIplot) and natural bonding orbital (NBO) methodologies. We believe the results reported herein will be useful for those scientists working in catalysis, molecular recognition and materials science fields, where structural-energetic relationships of weak interactions are crucial to achieve product selectivity, a particular molecular recognition mode or a specific molecular assembly. The relationship between Ag/Au nanoparticles (NPs) size and π-system extension has been evaluated at the PBE0-D3/def2-TZVP level of theory using 1-5 Ag/AuNPs and benzene, naphthalene and anthracene rings.