Isomeric 2, 2′-bipyridines 4a− 6a and 1, 10-phenanthrolines 7a− 9a with two diaminotriazinyl substituents have been synthesized, and structural studies have confirmed that they are likely to be rich sources of new supramolecular chemistry, based on their well- defined molecular topologies and their dual ability to chelate metals and form multiple hydrogen bonds according to reliable patterns.