New 4'-functionalized 2,2':6',2''-terpyridines for applications in macromolecular chemistry and nanoscience

The well-known reaction of 4'-chloro-2,2':6',2''-terpyridine with alkoxide nucleophiles leads to 4'-functionalized 2,2':6',2''-terpyridines. This reaction allows the easy introduction of different functional groups onto the terpyridine at the 4'-position, i.e., opposite to the metal binding site, in one reaction step. Among the functionalized 2,2':6',2''-terpyridines reported here are amines (including chiral examples), carboxylic acids, simple alkoxy-chain terpyridines with different chain lengths, and a stilbene-functionalized terpyridine (I). Moreover, the synthesis of two important already known substances was significantly improved. One example of a sequential functionalization of an (aminopentoxy)terpyridine with a dithiolane functionality, yielding II, is also reported. For two of the alkoxy-chain-functionalized terpyridines, single-crystal x-ray crystallog. data were obtained. Finally, ordered monolayers of alkoxy-substituted terpyridines III (n = 11, 17) on highly ordered pyrolytic graphite were visualized using STM. [on SciFinder (R)]