Modular Construction of Porous Hydrogen‐Bonded Molecular Materials from Melams
Tinasadat Khadivjam, Huy Che‐Quang, Thierry Maris, Zvart Ajoyan, Ashlee J. Howarth, James D. Wuest
Abstract
Abstract 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.