Article,

Ligand-Directed Molecular Architectures: Self-Assembly of Two-Dimensional Rectangular Metallacycles and Three-Dimensional Trigonal or Tetragonal Prisms

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Journal of the American Chemical Society, 125 (28): 8595--8613 (2003)
DOI: 10.1021/ja034267k

Abstract

Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene, L1, 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene, L2, and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, L3) and one tripodal ligand, 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene, L4, were prepd. Reaction of these shape-specific designed ligands with different metal salts affords discrete mol. architectures: Ag2L12(BF4)2 (1), Ag2L22(CF3SO3)2 (2), CF3SO3- $\subset$ Ag2L32CF3SO3 (3), CF3SO3- $\subset$ Ag2L33CF3SO3 (4), ClO4- $\subset$ Cu2L24(ClO4)3 (5), 4H2O $\subset$ Ni2L24Cl4·6H2O (6), BF4- $\subset$ Ag3L42(BF4)2 (7), ClO4- $\subset$ Ag3L42(ClO4)2 (8), and CuI32- $\subset$ Cu3L422Cu2I4 (9). The compds. were characterized by elemental anal., ESI-MS, IR, and NMR spectroscopy, and x-ray crystallog. 1 Is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L1 ligands are connected by two linearly coordinated Ag+ ions. 2 And 3 are structurally related, consisting of rectangular structures assembled from two linearly coordinated Ag+ ions and two L2 or L3 ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag+ ions in trigonal planar coordination linked by three L3 ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu2+ or Ni2+ ions linked by four L2 ligands. The topologies of 7-9 are similar to that of 4; however, these three structures are assembled from three linearly coordinated Ag+ or Cu+ ions and two tripodal ligands, representing an alternative strategy to assembling a trigonal prism. 1H NMR and ESI-MS were used to elucidate the soln. structures of these macrocycles. on SciFinder(R)

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