Dithienophosphole‐Based Phosphinamides with Intriguing Self‐Assembly Behavior

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.