DFT calculations predict that inverted geometries at carbon can be stabilized within multi-component co-crystals

• Published in: Theoretical chemistry accounts Vol. 142; no. 3
• Main Authors: Mandal, Sucharita, Datta, Ayan
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.03.2023; Springer Nature B.V
• Subjects: Aromatic compounds; Atomic/Molecular Structure and Spectra; Carbon; Chemistry; Chemistry and Materials Science; Crystals; Hydrogen bonding; Inorganic Chemistry; Organic Chemistry; Physical Chemistry; Theoretical and Computational Chemistry; Propellane; Halogen bonding; Crystal Engineering; Non-covalent Interactions; Inverted carbons; Hydrogen bonding; Density functional theory (DFT); Co-crystal
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-023-02966-1

Molecules with inverted carbon geometries like [1.1.1] and [2.2.2]-propellanes have been a subject of great interest from theoretical viewpoint. Nevertheless, experimental detection and isolation has been a challenge due to their transient nature. In this article, it is shown that halogen bonding of the radical centers with bromo and iodo-arenes can bestow stability to the system. Decorating these halogen-bonded propellanes with additional I…S halogen-bonding and N–H…O hydrogen bonding leads to the formation of highly robust multi(four)-component co-crystals of [1.1.1] and [2.2.2]-propellanes. Such multi-component co-crystals are proposed as stabilizing crystalline matrices for isolating fleeting stable intermediates/species.