N. Biot, D. Bonifazi.
Chem. Eur. J. 2020, 26, 2904.
The engineering of crystalline molecular solids through the simultaneous combination of distinctive non‐covalent interactions is an important field of research as it could allow chemist to prepare materials depicting multiresponsive properties. It is in this contest that, pushed by our will to expand the chemical space of chalcogen‐bonding interactions that, in this work we put forward the concept for which chalcogen‐ and halogen‐bonding interactions can be used simultaneously to engineer multicomponent co‐crystals. Through the rational design of crystallizable molecules, we prepared chalcogenazolo pyridine scaffold (CGP) modules that, bearing either a halogen‐bond acceptor or donor at the 2‐position can interact with suitable complementary molecular modules, undergoing formation of supramolecular polymers at the solid state. The recognition reliability of the CGP moiety to form chalcogen‐bonded dimers allow the formation heteromolecular supramolecular polymers through halogen‐bonding interactions as confirmed by single‐crystal X‐ray diffraction analysis.