Corundum, diamond, and PtS metal-organic frameworks with a difference: self-assembly of a unique pair of 3-connecting D2d-symmetric 3,3',5,5'-tetrakis(4-pyridyl)bimesityl.

There is an upsurge of interest in the synthesis of coordination polymers in contemporary supramolecular chemistry, as coordination polymerization may lead to materials with controllable functions such as porosity, sensing, nonlinear optical (NLO) activity, and chirality. Crystal engineering based on predesigned organic linkers and metal centers (building blocks) with specific coordination geometries is an important approach in the preparation of coordination materials with desired functions. Based on the knowledge of the structures of the ligands and the coordination geometries of a variety of metal centers, diverse 2D and 3D nets—several of which are analogous to structures of inorganic materials—have been engineered in the field of metal–organic frameworks (MOFs). Thus, the syntheses of 3connected nets corresponding to the topologies of SrSi2/(10,3)-a, ThSi2/(10,3)-b, [4] (12,3), (3,4)-connected nets with the topologies of boracite, Cu15Si4, [7] (5,4), [8] and (3,6)connected nets corresponding to the topologies of rutile and pyrite have been accomplished. Insofar as the 4connected nets are concerned, the syntheses of MOFs with unusual topologies and with topologies corresponding to those of diamond, NbO, quartz, and PtS have been reported. Similarly, the (4,8)and 6-connected metal– organic frameworks with fluorite and cubic topologies, respectively, have been designed and synthesized. In view of the success of such building-block approaches to realize metal–organic frameworks with specific topologies, the multidentate ligands with novel structural features offer the possibility to construct new and unique coordination poly-