Selective host-guest interaction between metal ions and metal-organic frameworks using dynamic nuclear polarization enhanced solid-state NMR spectroscopy

Chemistry. 2014 Dec 1;20(49):16308-13. doi: 10.1002/chem.201403884. Epub 2014 Oct 8.

Abstract

The host-guest interaction between metal ions (Pt(2+) and Cu(2+) ) and a zirconium metal-organic framework (UiO-66-NH2 ) was explored using dynamic nuclear polarization-enhanced (15) N{(1) H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt(2+) coordinates with two NH2 groups from the MOF and two Cl(-) from the metal precursor, whereas Cu(2+) do not form chemical bonds with the NH2 groups of the MOF framework. Density functional calculations reveal that Pt(2+) prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

Keywords: X-ray absorption spectroscopy; density functional calculations; dynamic nuclear polarization; metal-organic frameworks; solid-state NMR spectroscopy.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Copper / chemistry*
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Organometallic Compounds / chemistry*
  • Platinum / chemistry*
  • X-Ray Absorption Spectroscopy
  • Zirconium / chemistry*

Substances

  • Organometallic Compounds
  • Platinum
  • Copper
  • Zirconium