Zn(II)-Siloxane Clusters as Versatile Building Blocks for Carboxylate-Based Metal-Organic Frameworks

Siloxanes have long been known for their highly desirable properties suited for a wide range of practical applications; however, their utilization as modular building blocks for crystalline open frameworks has been limited. In this study, a simple solvothermal pathway has been found to synthesize unprecedented Zn(II)-siloxane clusters supported by acetate ligands, [(RSiO₂)₈Zn₈(CH₃CO₂)₈] (R = Me or Ph). The same reaction using a dicarboxylate ligand such as 1,4-benzenedicarboxylate or 2,6-naphthalenedicarboxylate produces a new type of metal-organic framework, named SiMOF here, based on the [Si₈Zn₈] units. With the maximum connectivity of 8, the building block is shown to form topologically interesting structures such as octahedral supercages or uninodal 8-connected frameworks. All SiMOFs synthesized possess permanent porosity and high thermal stability and are naturally hydrophobic, as demonstrated by adsorptions of toluene, ethanol, methanol, and water vapor as well as water contact angle measurements. These promising characteristics for well-defined porous solids are attributed to metal-bound siloxane groups in the structural building units.