Three-fold-Interpenetrated Diamondoid Coordination Frameworks with Torus Links Constructed by Tetranuclear Building Blocks

Two new isostructural coordination polymers, namely, [M(malo)(HFlu)]n (M = Zn for 1 and Cu for 2, malo = malonate dianion, HFlu = fluconazole), have been prepared by a solution diffusion method. The polymers show rare three-dimensional 3-fold interpenetrated dia-f coordination frameworks with (2.2.1) Hopf links and (6.3.3) Torus links. The tetranuclear M4(malo)4 cluster as a secondary building unit becomes the decorated vertex in the dia-f net. Polymer 1 shows an intense fluorescent emission, while polymer 2 shows a quenching phenomenon in the solid state at room temperature. Magnetic susceptibility studies for 2 reveal a ferromagnetic coupling interaction in the anti-syn carboxylate-bridged Cu(II) clusters. Comparable experiments with Ni(II) and Cd(II) resulting in discrete dinuclear structures are also reported.