A Designed Three-Dimensional Porous Hydrogen-Bonding Network Based on a Metal–Organic Polyhedron

By employment of sulfonate-decorated metal–organic cuboctahedra (MOCs) as tectons, we report an interesting example of molecular tectonics strategy for the rational construction of three-dimensional (3D) porous network 1 through complementary and metrically matched N–H+···–O–S hydrogen bonds between guanidinium and sulfonate (GS) moieties. Built from the MOCs as 24-connected nodes and the GS H-bonding motifs as 3-connected nodes, 1 was expected to have a (3,24)-connected network topology, which has been verified by the single crystal X-ray analysis. In addition, the porous H-bonding network 1 displays good stability under ambient conditions and modest absorption of cationic dye molecules.