A 3D Canted Antiferromagnetic Porous Metal−Organic Framework with Anatase Topology through Assembly of an Analogue of Polyoxometalate

The unique porous metal−organic framework {KCo3(C6H4O7)(C6H5O7)(H2O)2·8H2O}8 (1), which exhibits an unprecedented infinite 3D (3,6)-connected decorated anatase net, has been obtained by hydrothermal reaction. Upon dehydration, the compound retains crystallinity and exhibits a type I N2 sorption isotherm, characteristic of a microporous solid with apparent Langmuir surface area 939 m2/g and pore volume 0.31 cm3/g. Magnetic measurements for both 1 and dehydrated 1 show the spin-canted antiferromagnetic state below 5 K and a magnetic hysteresis loop at 2 K. Thus, dehydrated 1 represents the first metal−organic framework for which microporosity and a spin-canted antiferromagnetic state coexist, which demonstrates that the self-assembly of organo-polymetal clusters and metal ions can provide a potential route to magnetic porous metal−organic frameworks.