C(3i)-symmetric octanuclear cadmium cages: double-anion-templated synthesis, formation mechanism, and properties

Chemistry. 2012 Dec 14;18(51):16525-30. doi: 10.1002/chem.201200980. Epub 2012 Oct 4.

Abstract

A series of C(3i)-symmetric bicapped trigonal antiprismatic Cd(8) cages [2X@Cd(8)L(6)(H(2)O)(6)]⋅n Y⋅solvents (X = Cl(-), Y = NO(3)(-), n = 2: MOCC-4; X = Br(-), Y = NO(3)(-), n = 2: MOCC-5; X = NO(3)(-), Y = NO(3)(-), n = 2: MOCC-6; X = NO(3)(-), Y = BF(4)(-), n = 2: MOCC-7; X = NO(3)(-), Y = ClO(4)(-), n = 2: MOCC-8; X = CO(3)(2-), n = 0: MOCC-9), doubly anion templated by different anions, were solvothermally synthesized by means of a flexible ligand. Interestingly, the CO(3)(2-) template for MOCC-9 was generated in situ by two-step decomposition of DMF solvent. For other MOCCs, spherical or trigonal monovalent anions could also play the role of template in their formation. The template abilities of these anions in the formation of the cages were experimentally studied and are discussed for the first time. Anion exchange of MOCC-8 was carried out and showed anion-size selectivity. All of the cage-like compounds emit strong luminescence at room temperature.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry*
  • Cadmium / chemistry*
  • Crystallography, X-Ray
  • Ligands
  • Luminescence
  • Macromolecular Substances / chemical synthesis*
  • Macromolecular Substances / chemistry*
  • Models, Molecular
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Temperature

Substances

  • Anions
  • Ligands
  • Macromolecular Substances
  • Organometallic Compounds
  • Cadmium