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Alkali metal ion complexes of functionalised calixarenes--competition between pendent arm and anion bonding to sodium. | LitMetric

AI Article Synopsis

  • The study determined the crystal structure of a complex made from sodium triflate and a modified calix[4]arene, revealing unexpected results regarding its interaction with sodium ions.
  • Contrary to expectations, the calix[4]arene's diether arms do not coordinate with the sodium cation, but the framework adopts a nearly symmetrical shape due to the coordination of phenolic oxygen atoms.
  • Monoclinic crystals were grown from acetonitrile at low temperature (153 K), helping to overcome challenges faced at higher temperatures and suggesting that the orientations of substituents and anions may change with temperature.

Article Abstract

Determination of the crystal structure of the acetonitrile inclusate of the complex formed between sodium trifluoromethanesulfonate (triflate, CF3SO3-) and the narrow-rim functionalised calix[4]arene, 5,11,17,23-tetra-tert-butyl-25,27-di(phenylmethoxy)-26,28-di(2'-methoxyethoxy)calix[4]arene, has shown, somewhat unexpectedly, that the diether pendent arms do not chelate the sodium cation, although coordination of all four phenolic oxygen atoms does draw the calixarene into a nearly symmetrical cone form, consistent with conclusions drawn earlier from solution 1H NMR data. Crystals of C64H80O6.NaO3S.CF3.CH3CN obtained from acetonitrile solvent are monoclinic, C2/c, a structure determination at 'low' temperature (153 K) resolving several difficulties encountered in earlier attempts to analyse data acquired at approximately 295 K, and indicative of an interesting temperature dependence of substituent and anion orientations.

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Source
http://dx.doi.org/10.1039/b307193fDOI Listing

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