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

• Published in: Journal of the American Chemical Society Vol. 125; no. 28; pp. 8595 - 8613
• Main Authors: Su, Cheng-Yong, Cai, Yue-Peng, Chen, Chun-Long, Smith, Mark D, Kaim, Wolfgang, zur Loye, Hans-Conrad
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 16.07.2003; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Condensed matter: structure, mechanical and thermal properties; Coordination compounds; Exact sciences and technology; Inorganic chemistry and origins of life; Inorganic compounds; Metal complexes; Physical Sciences; Physics; Preparations and properties; Science & Technology; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; CYCLIC NANOSTRUCTURES; COPPER(II) COMPLEXES; CAGE-LIKE COMPLEX; NANOPOROUS NETWORK; TRIPLE-STRANDED HELICATE; SILVER(I) COMPLEXES; COORDINATION POLYMERS; ELECTROSPRAY MASS-SPECTROMETRY; SOLID-STATE; RATIONAL DESIGN; Cationic complex; Molecular packing; Nickel Complexes; Silver Complexes; Trinuclear complex; Organic ligand; NMR spectrometry; Inorganic synthesis; Transition metal Complexes; Copper Complexes; X ray diffraction; Molecular assembly; Supramolecular structure; Dinuclear complex; Polynuclear complex; Mass spectrometry; Halo complex; Crystalline structure
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja034267k

Three angular ditopic ligands (1,3-bis(benzimidazol-1-ylmethyl)-4,6-dimethylbenzene L 1 , 1,3-bis(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 2 , and 1,4-bis(benzimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene L 3 ) and one tripodal ligand 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene L 4 have been prepared. Reaction of these shape-specific designed ligands with different metal salts affords a series of discrete molecular architectures:  [Ag2 L 1 2](BF4)2 1, [Ag2 L 2 2](CF3SO3)2 2, [CF3SO3 - ⊂ Ag2 L 3 2]CF3SO3 3, [CF3SO3 - ⊂ Ag2 L 3 3]CF3SO3 4, [ClO4 - ⊂ Cu2 L 2 4](ClO4)3 5, [4H2O ⊂ Ni2 L 2 4Cl4]·6H2O 6, [BF4 - ⊂ Ag3 L 4 2](BF4)2 7, [ClO4 - ⊂ Ag3 L 4 2](ClO4)2 8, and [CuI3 2- ⊂ Cu3 L 4 2]2[Cu2I4] 9. The compounds were characterized by elemental analysis, ESI-MS, IR, and NMR spectroscopy, and X-ray crystallography. 1 is a dinuclear metallacycle with 2-fold rotational symmetry in which two syn-conformational L 1 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 L 2 or L 3 ligands. The structure of 4 is a trigonal prismatic box consisting of two Ag+ ions in trigonal planar coordination linked by three L 3 ligands, while the structures of 5 and 6 are tetragonal prismatic cages constructed by two square planar Cu2+ or Ni2+ ions linked by four L 2 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 utilized to elucidate the solution structures of these macrocycles.