NMR Complexation Study of Several Oxyethylated Calix[4]arenes with Lithium, Sodium and Potassium Ions

Abstract

The influence of calix[4]arene upper rim substitution on the complexation with Li+, Na+, K+ was studied by 1H NMR spectroscopy. Calix[4]arenes 1-4 namely 25,26,27,28-tetrakis(3-oxapentyloxy)calix[4]arene (1), its 5,17-diamino (2) and 5,17-dinitro derivative (3) as well as 25,26,27,28-tetrakis(3,6,9-trioxadecyloxy)calix[4]arene (4) having four monoalkyloligoethylene glycol chains on the lower rim have been studied. No complexation has been observed for Li+. Two electron-donating NH2 groups on the calixarene upper rim (compound 2) improve the complexation ability for Na+ and K+ compared with parent calixarene 1. The electron-withdrawing nitro groups in 3 have the opposite influence. It seems that the complexation of alkali metal ions studied is not significantly influenced by the increasing number of donor atoms (from eight in 1 to sixteen in 4) available for complexation on the lower rim. The position of sodium cation in 1 . Na+ and 4. Na+ is supposed to be in close proximity of phenolic oxygens based on 1H and 13C NMR data. The error analysis is given for the stability constant determination from NMR data.