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

Five peri-substituted naphthalene and acenaphthalene complexes (Ph(2)Pn)(2)Naph (E=Sb 1, Bi 3), (Ph2Sb)(2)Acenaph (2), (Ph2Bi)(Me3Sn)Naph (4) and (PhBiNaph)(2) (5) were synthesized and characterized in solution (H-1, C-13 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...pi, pi....pi and Bi....pi (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....pi contact provides the main stabilizing contribution. Symmetry-adapted intermolecular perturbation theory calculations showed that this and other contacts are dominated by London dispersion interactions.

Automated summary

Five peri-substituted naphthalene and acenaphthalene complexes were synthesized and characterized, showing different types of noncovalent intermolecular interactions in the solid-state. Density functional theory calculations demonstrated that the Bi....pi contact provided the main stabilizing contribution, with London dispersion interactions dominating these contacts.