Modular Construction of Porous Hydrogen-Bonded Molecular Materials from Melams

Ordered materials with predictable structures and properties can be made by a modular approach, using molecules designed to interact with neighbors and hold them in predetermined positions. Incorporating 4,6-diamino-1,3,5-triazin-2-yl (DAT) groups in modules is an effective way to direct assembly because each DAT group can form multiple N-H⋅⋅⋅N hydrogen bonds according to established patterns. We have found that modules with high densities of N(DAT)₂ groups can be made by base-induced double triazinylations of readily available amines. The resulting modules can form structures held together by remarkably large numbers of hydrogen bonds per molecule. Even simple modules with only 1-3 N(DAT)₂ groups and fewer than 70 non-hydrogen atoms can crystallize to form highly open networks in which each molecule engages in over 20 N-H⋅⋅⋅N hydrogen bonds, and more than 70 % of the volume is available for accommodating guests. In favorable cases, guests can be removed to create rigorously porous crystalline solids analogous to zeolites and metal-organic frameworks.