Noncovalent Intra‐ and Intermolecular Interactions in Peri‐Substituted Pnicta Naphthalene and Acenaphthalene Complexes

Abstract Five peri‐substituted naphthalene and acenaphthalene complexes (Ph 2 Pn) 2 Naph (E=Sb 1 , Bi 3 ), (Ph 2 Sb) 2 Acenaph ( 2 ), (Ph 2 Bi)(Me 3 Sn)Naph ( 4 ) and (PhBiNaph) 2 ( 5 ) were synthesized and characterized in solution ( 1 H, 13 C NMR, IR) and in the solid‐state (sc‐XRD). 1–5 show different types of noncovalent intermolecular interactions in the solid‐state including Naph−H⋅⋅⋅π, π⋅⋅⋅π and Bi⋅⋅⋅π ( 5 ) contacts, which were exemplarily ( 5 ) quantified by use of density functional theory and local coupled cluster electronic structure theory calculations, demonstrating that the Bi⋅⋅⋅π contact provides the main stabilizing contribution. Symmetry‐adapted intermolecular perturbation theory calculations showed that this and other contacts are dominated by London dispersion interactions.