Various Stacking Patterns of Two‐Dimensional Molecular Assemblies in Hydrogen‐Bonded Cocrystals: Insight into Competitive Intermolecular Interactions and Control of Stacking Patterns
Masaki Donoshita, Yukihiro Yoshida, Mikihiro Hayashi, Ryuichi Ikeda, Susumu Tanaka, Yasuhisa Yamamura, Kazuya Saito, Shogo Kawaguchi, Kunihisa Sugimoto, Hiroshi Kitagawa
Abstract
Control over the stacking patterns in 2D molecular assemblies is demonstrated using chemical modification. A target system is a hydrogen-bonded cocrystal (2:1) composed of 2-pyrrolidone (Py) and chloranilic acid (CA) (PyCA). X-ray crystallography showed that weak intersheet interactions give rise to a variety of metastable overlapping patterns comprised of the 2D assemblies mainly formed via hydrogen bonds, affording reversible and irreversible structural phase transitions. We prepared cocrystals of Py and anilic acids bearing different halogens, in which 2D assemblies isostructural with those observed in PyCA exhibit various overlapping patterns. The order of stability for each overlapping pattern estimated using calculations of the intermolecular interactions did not completely coincide with those indicated by our experimental results, which can be explained by considering the entropic effect: the molecular motion of Py as detected using nuclear quadrupole resonance spectroscopy.