Microporous networks co-assembled by both rigid and flexible building blocks

Abstract The porous networks of [Cu 2 (malonato) 2 (bipy)(H 2 O) 2 ]·H 2 O ( I ) and [Cd(malonato)(py)(H 2 O)] ( II ) were co-assembled by rigid 4,4′-bipyridine or pyridine and the flexible malonate ion. In the network of compound I , 4,4′-bipy acts as a bone, separating and supporting the flexible malonate–Cu units to form a nearly strain-free square framework and a chiral square cavity in the solid state. In compound II , the rigid pyridine rings sustain the network by saturating the coordination sphere of Cd(II) ion to avoid a high coordination number and self-inclusion, and to prevent the two-dimensional network from forming a non-porous phase.