Dithienophosphole-Based Phosphinamides with Intriguing Self-Assembly Behavior

Abstract

A new, highly adaptable type of phosphinamide-based hydrogen bonding is representatively demonstrated in π-conjugated phosphole materials. The rotational flexibility of these intermolecular P=O-H-N hydrogen bonds is demonstrated by X-ray crystallography and variable-concentration NMR spectroscopy. In addition to crystalline compounds, phosphinamide hydrogen bonding was successfully introduced into the self-assembly of soft crystals, liquid crystals, and organogels, thus highlighting the high general value of this type of interaction for the formation of organic soft materials. New HOPe: Dithienophosphole-based phosphinamides (see structure) display rotationally flexible hydrogen bonding that contrasts with that of their carboxamide cousins. Besides the novel hydrogen-bonding motif, these compounds also demonstrated unique photophysical and amphiphilic properties as a result of hydrogen-bond-directed self-assembly.