Synthesis of conjugatively bridged bis- and tris-5-(2,2′-bipyridines):: Multitopic metal ion-binding modules for supramolecular nanoengineering

An efficient preparation of linear and curved bis- and branched tris-5-(2,2'-bipyridines) of nanoscopic dimensions possessing rigid conjugated bridges is presented. The synthesis, which avoids the need of protection/deprotection methodology, utilizes central bridge precursors which are outwardly di-and trifunctionalized with a 5-(2-chloropyridine) synthon via a chemoselective palladium-catalyzed Sonogashira or Negishi cross-coupling protocol to yield the bridged linear (5a-c, 5f,g) and curved (6, 7) bis- and branched (8) tris-5-(2-chloropyridines). Under more forcing conditions, the ethyne-bridged 5-(2-chloropyridines) undergo the Stille cross-coupling reaction with 2-trimethylstannylpyridines to afford the conjugatively bridged linear (1a,b, 1g-j) and curved (2a,b, 3a,b) bis- and branched, (4a,b) tris-5-(2,2'-bipyridines) in good overall yields. The phenyl- and biphenyl-bridged linear bia-5-(2,2'-bipyridines) (1c-f) were best prepared from the bis-5-(2-bromopyridines) (5d,e) to ensure completion of the Stille cross-coupling reactions. The Stille cross-couplings showed a marked substituent effect in which the terminally phenylated bis- and tris-5-(2,2'-bipyridines) were formed in higher yields than the methyl-substituted analogues with the same bridge. The advantages of the methodology lie in its synthetic convenience and adaptibility for creating multitopic metal ion-binding scaffolds with a potentially very large variety of bridging units and substituents on the terminal pyridine rings. The bridged 5-(2-chloropyridines) may also serve as precursors for the fabrication of metal ion-coordinated conjugated polymers.