Multidentate, V-Shaped Pyridine Building Blocks as Tectons for Crystal Engineering

The formation of supramolecular structural units through self-assembly is a powerful method to design new architectures and materials endowed with specific properties. With the aim of adding a group of versatile tectons to the toolkit of crystal engineers, we have devised and synthesised four new V-shaped building blocks characterised by an aryl acetylene scaffold comprising three substituted pyridine rings connected by two triple bonds. The judicious choice of different substituents on the pyridine rings provides these tectons with distinctive steric, electrostatic and self-assembly properties, which influence their crystal structures and their ability to form co-crystals. Co-crystals of the tectons with tetraiododifluorobenzene were obtained both via traditional and mechanochemical crystallisation strategies, proving their potential use in crystal engineering. The energetic contributions of the supramolecular interactions at play in the crystal lattice have also been evaluated to better understand their nature and strength and to rationalise their role in designing molecular crystals.

Automated summary

The formation of supramolecular structural units through self-assembly is a powerful method for designing new architectures and materials. We synthesized four new V-shaped building blocks with distinctive properties, which formed co-crystals with tetraiododifluorobenzene, demonstrating potential applications in crystal engineering. The energetic contributions of the supramolecular interactions in the crystal lattice were evaluated to understand their nature and rationalize their role in designing molecular crystals.