Metal-Ion Metathesis and Properties of Triarylboron-Functionalized Metal-Organic Frameworks

An anionic metal-organic framework, H-3[(Mn4Cl)(3)L-8]30H(2)O2.5DMF5Diox (UPC-15), was successfully prepared by the reaction of MnCl2 with tris(p-carboxylic acid)tridurylborane (H3L) under solvothermal conditions. UPC-15 with wide-open pores (approximate to 18.8 angstrom) is constructed by packing of octahedral and cuboctahedral cages, and exhibits high gas-sorption capabilities. Notably, UPC-15 shows selective adsorption of cationic dyes due to the anion framework. Moreover, the catalytic and magnetic properties were investigated, and UPC-15 can highly catalyze the cyanosilylation of aromatic aldehydes. UPC-15 exhibits the exchange of metal ions from Mn to Cu in a single-crystal-to-single-crystal manner to generate UPC-16, which could not be obtained by the direct solvothermal reaction of CuCl2 and H3L. UPC-16 exhibits similar properties for gas sorption, dye separation, and catalytic activity. However, the magnetic behaviors for UPC-15 and UPC-16 are distinct due to the metal-specific properties. Below 47K, UPC-15 exhibits a ferromagnetic coupling but UPC-16 shows a dominant antiferromagnetic behavior.