Isomeric molecular rectangles resulting from self-assembly of dicopper complexes of macrocyclic ligands

Inorg Chem. 2006 Mar 20;45(6):2501-8. doi: 10.1021/ic051759k.

Abstract

Dinuclear copper complexes containing hexaazacyclophane macrocyclic ligands react with the disodium salt of terephthalic acid resulting in the self-assembly of rectangular molecules with the general formula [(Cu2L)2(p-(O2CC6H4CO2)2)]X4, where X = CF3SO3 and ClO4 (3X4, L = Me2p and 4X4, L = Me2m). Tetranuclear complexes 3(CF3SO3)4 (as polymorphs 3a and 3b) and 4(ClO4)4 have been characterized by single-crystal X-ray diffraction analysis providing definitive proof of their structure as well as their metrical parameters. 3a contains, in its unit cell, two isomeric cationic units (3asyn and 3aanti) that differ in the relative position of the two O carboxylate atoms which bind to the Cu atoms of the different macrocyclic complexes, leading to boxes with different metrical parameters. ESI-MS analyses of solutions of the tetranuclear complexes 3(CF3SO3)4 and 4(CF3SO3)4 exhibit cluster ions which match the solid state formulation, thus demonstrating that the cages are retained in solution.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Copper / chemistry*
  • Crystallography, X-Ray
  • Heterocyclic Compounds / chemistry*
  • Ligands
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Spectrometry, Mass, Electrospray Ionization

Substances

  • Heterocyclic Compounds
  • Ligands
  • Organometallic Compounds
  • Copper