Temperature-dependent IR spectroscopic and structural study of 18-crown-6 chelating ligand in the complexation with sodium surfactant salts and potassium picrate

Spectrochim Acta A Mol Biomol Spectrosc. 2014 Apr 24:124:12-20. doi: 10.1016/j.saa.2013.12.092. Epub 2014 Jan 2.

Abstract

18-crown-6 ether (18C6) complexes with the following anionic surfactants: sodium n-dodecylsulfate (18C6-NaDS), sodium 4-(1-pentylheptyl)benzenesulfonate (18C6-NaDBS); and potassium picrate (18C6-KP) were synthesized and studied in terms of their thermal and structural properties. Physico-chemical properties of new solid 1:1 coordination complexes were characterized by infrared (IR) spectroscopy, thermogravimetry and differential thermal analysis, differential scanning calorimetry, X-ray diffraction and microscopic observations. The strength of coordination between Na(+) and oxygen atoms of 18C6 ligand does not depend on anionic part of the surfactant, as established by thermodynamical parameters obtained by temperature-dependent IR spectroscopy. Each of these complexes exhibit different kinds of endothermic transitions in heating scan. Diffraction maxima obtained by SAXS and WAXS, refer the behavior of the compounds 18C6-NaDS and 18C6-NaDBS as smectic liquid crystalline. Distortion of 18C6-NaDS and 18C6-KP complexes occurs in two steps. Temperature of the decomplexation of solid crystal complex 18C6-KP is considerably higher than of mesophase complexes, 18C6-NaDS, and 18C6-NaDBS. The structural and liquid crystalline properties of novel 18-crown-ether complexes are function of anionic molecule geometry, type of chosen cation (Na(+), K(+)), as well as architecture of self-organized aggregates. A good combination of crown ether unit and amphiphile may provide a possibility for preparing new functionalized materials, opening the research field of ion complexation and of host-guest type behavior.

Keywords: 18-crown-6 ether; Anionic surfactants; IR spectroscopy; Liquid crystals; Thermal properties; X-ray diffraction.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chelating Agents / chemistry*
  • Crown Ethers / chemistry*
  • Differential Thermal Analysis
  • Ligands
  • Picrates / chemistry*
  • Salts / chemistry*
  • Sodium / chemistry*
  • Spectrophotometry, Infrared
  • Surface-Active Agents / chemistry*
  • Temperature*
  • Transition Temperature
  • X-Ray Diffraction

Substances

  • Chelating Agents
  • Crown Ethers
  • Ligands
  • Picrates
  • Salts
  • Surface-Active Agents
  • 18-crown-6
  • Sodium
  • picric acid