An Attempt to Programme the Orientation of Bis(heterocyclic) Azine Heterotopic Sequences around AgI, CuI and ZnII Metal Centres

Four novel bis(heterocyclic) sequences, which incorporate a 2,2′‐bipyridine system with the 2,2′‐bithiazole, 4,4′‐bithiazole, 2,2′‐bipyrazine or 4,4′‐bipyrimidine units, have been synthesized. In the presence of stoichiometric amounts of CuI, AgI or ZnII cations, fully oriented discrete head‐to‐head (H‐H) or head‐to‐tail (H‐T) species have been observed by NMR and X‐ray crystallography. The orientation of the ligands in the AgI, CuI or Zn II dinuclear complexes during the self‐assembly process appears to be under the control of electronic factors relating to the electronic configuration of the different bis(heterocyclic) sequences. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)