MECHANOCHEMICAL PATHWAYS FROM COORDINATION POLYMERS TO MOFS: STEPWISE STUDY ON FRAMEWORKS EXPANSION

Mechanochemistry has been recognized by IUPAC as one of the "Ten Chemical Innovations That Will Change Our World"[1], and its popularity continues to grow due to its ability to translate solution-based synthetic protocols into solvent-free conditions while enabling novel synthetic strategies.[2] In particular, mechanochemistry is highly effective for MOF synthesis, providing a rapid, simple, and high-yield alternative to traditional solvothermal methods, significantly reducing solvent consumption and environmental impact. In this work, we explore the stepwise construction of a framework entirely in the solid state. We first synthesize a coordination polymer in a one-pot reaction, selecting a well-known Zn(II)-based framework of general formula Zn(II)ₓ(acetate)ᵧ(1,2-(4-pyridyl)-ethylene)𝓏, where x,y,z are depend on the reaction conditions. Its synthesis can be finely tuned by adjusting reagent stoichiometry and liquid-assisted grinding (LAG) conditions, yielding three distinct products quantitatively and with reaction times significantly shorter than those reported for solution-based methods. Building on this approach, we introduce a second ligand sequentially to obtain a pillared MOF via a one-pot, two-step process and compare it with a direct one-pot, two-step synthesis. [1] Fernando Gomollón-Bell, Chemistry International (2019), 41, 12– 17. [2] Tomislav Friščić, Cristina Mottillo, and Hatem M. Titi, Angewandte Chemie Int. Ed. (2020), 59, 1018–1029.