Ultra-Thin 2D Ionic Salt Supported with Strong Hydrogen-Bonding Assisted Ionic Interaction.

2D materials have attracted great interest since the report of graphene. However, because of the fragile stability of ultra-thin nanosheets, most studies are restricted to sheets maintained by strong covalent or coordination bonds. The research on which kind of bonds can maintain the free-standing existence of 2D nanosheets is still of great significance. Recently, 2D ionic salts are successfully synthesized on substrates, but whether 2D ionic salts can free-stand is still a problem. Herein this problem is addressed by a free-standing 2D ionic salt (thickness: ≈2 nm) exfoliated from a 4,4'-bipyridinium hydrochloride salt crystal. The stability of this 2D salt is supported by a strong NH···Cl hydrogen (H)-bonding assisted ionic interaction (17.99 kcal mol ), which is verified by density functional theory calculation and natural bond orbital analysis. The salt crystal has strong air-stable radicals inside and the 2D ionic salt exhibits red fluorescence in solution and in solid-state, especially in solution the stokes shifts are very large (≈ 386 nm). This breakthrough work is not only beneficial for the construction of novel 2D materials but also for the understanding of H-bonding interactions.