Direct and Telescopic Mechanochemical Synthesis of Higher-order Organic-Inorganic Hybrid Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design

Abstract

The ability to rationally design and predictably construct crystalline solids has been the hallmark of crystal engineering research over the past two decades. When building higher-order multicomponent cocrystals (i.e. crystals containing more than two constituents), the differential and hierarchical way molecules interact and assemble in the solidstate is of pinnacle importance. To date, numerous examples of multicomponent crystals comprising organic molecules leading to salts, cocrystals or ionic cocrystals have been reported. However, the crystal engineering of hybrid organicinorganic cocrystals with sophisticated inorganic building blocks is still poorly understood and mostly unexplored. Here, we reveal the first efficient mechanochemical synthesis of higher-order hybrid organic-inorganic cocrystals based on the structurally versatile – yet largely unexplored – cyclodiphos(V/V)azane heterosynthon building block. The novel hybrid ternary and quaternary multicomponent cocrystals herein reported are held together by synergistic intermolecular interactions (e.g., hydrogen- and halogen-bonding, Se-π and ion-dipole interactions). Notably, higher-order ternary and quaternary cocrystals can be readily obtained either via direct synthetic routes from its individual components, or via unprecedented telescopic approaches from lower-order cocrystal sets. In addition, computational modelling has also revealed that the formation of higher-order cocrystals is thermodynamically driven, and that bulk moduli and compressibilities are strongly dependent on the chemical composition and intermolecular forces present in the crystals, which offer untapped potential for optimizing material properties.

Mechanochemical synthesis of metal oxide nanoparticles

“…Metal organic frameworks 33 , organometallic complexes 34,35 and organic compounds 29,36 can also be produced using mechanochemistry. Moreover, the production of complex structures 37 such as hybrid materials consisting of a core of inorganic materials and a shell of organic materials 38 was demonstrated by mechanochemical processing. The usefulness of mechanochemical processing to produce nanostructured materials was also recognised at an early development stage of nanotechnology 39 .…”