Porous anionic, cationic, and neutral metal-carboxylate frameworks constructed from flexible tetrapodal ligands: syntheses, structures, ion-exchanges, and magnetic properties

Inorg Chem. 2011 Mar 21;50(6):2264-71. doi: 10.1021/ic1019229. Epub 2011 Feb 8.

Abstract

A series of coordination polymers with anionic, cationic, and neutral metal-carboxylate frameworks have been synthesized by using a flexible tetrapodal ligand tetrakis[4-(carboxyphenyl)oxamethyl] methane acid (H(4)X). The reactions between divalent transition-metal ions and H(4)X ligands gave [M(3)X(2)]·[NH(2)(CH(3))(2)](2)·8DMA (M = Co (1), Mn (2), Cd(3)) which have anionic metal-carboxylate frameworks with NH(2)(CH(3))(2)(+) cations filled in channels. The reactions of trivalent metal ions Y(III), Dy(III), and In(III) with H(4)X ligands afforded cationic metal-carboxylate frameworks [M(3)X(2)·(NO(3))·(DMA)(2)·(H(2)O)]·5DMA·2H(2)O (M = Y(4), Dy(5)) and [In(2)X·(OH)(2)]·3DMA·6H(2)O (6) with the NO(3)(-) and OH(-) serving as counterions, respectively. Moreover, a neutral metal-carboxylate framework [Pb(2)X·(DMA)(2)]·2DMA (7) can also be isolated from reaction of Pb(II) and H(4)X ligands. The charged metal-carboxylate frameworks 1-5 have selectivity for specific counterions in the reaction system, and compounds 1 and 2 display ion-exchange behavior. Moreover, magnetic property measurements on compounds 1, 2, and 5 indicate that there exists weak antiferromagnetic interactions between magnetic centers in the three compounds.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry
  • Carboxylic Acids / chemistry*
  • Cations / chemistry
  • Crystallography, X-Ray
  • Ligands
  • Magnetics*
  • Metals, Heavy / chemistry*
  • Models, Molecular
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Porosity
  • Surface Properties

Substances

  • Anions
  • Carboxylic Acids
  • Cations
  • Ligands
  • Metals, Heavy
  • Organometallic Compounds