Structural properties of [Cu()L] cages: bridged polyatomic anion effects on unprecedented efficiency of heterogeneous catechol oxidation

Self-assembly of CuX 2 (X − = BF 4 − , ClO 4 − , PF 6 − , and SbF 6 − ) with a bidentate ethylmethylbis(3-pyridine)silane ligand (L) in the presence of additional polyatomic anions (X′ = SiF 6 2− and PF 6 − ) gives rise to single crystals consisting of the X′@[Cu( ii ) 3 L 6 ] cage motif. These cages exist as discrete or anion-bridged 3D networks depending on outside anions. The anion-bridged 3D networks interpenetrate in a four-fold fashion, and show, to our best knowledge, the most effective heterogeneous catalysis in 3,5-di- tert -butylcatechol oxidation reaction within 20 min at room temperature. Surprisingly, the heterogeneous catalysis is more effective than its corresponding homogeneous catalysis. Such notable catalytic effects can be explained by the maintenance of 3D inter-cage Cu Cu distance as a catalytic center. Discrete cages or a 4-fold 3D network of Cu 3 L 4 units were constructed depending on the metallophilicity of outside anions. Interestingly, the heterogeneous catalysis is much more effective than its corresponding homogeneous catalysis.