Beryllium(II) Recognition by Allosteric Effects in 1,2-Ethylenedioxybenzene Based Ditopic Receptors

Efficient ditopic receptor, uranyl(II) N,N'-(ethylenedioxy)benzenebis(salicylideneimine) (3) for beryllium ion has been obtained upon functionalization of 1,2-ethylenedioxybenzene (1) with a uranyl-salphen (salphen = N,N'-phenylenebis(salicylideneimine)) unit. Binding affinities of the receptor, 3 in AN-DMSO (v/v 95:5) solution have been measured for alkali and alkaline earth metal ions by conductometry comparing 1. The results showed that both monotopic 1 and ditopic receptor 3 were selective for $Be^{2+}$ ions over other cations, while especially 3 that can complex both with cations (coordinated to basic oxygen of ethylenedioxybenzene) and anions (coordinated to the Lewis acidic uranyl center) results in an increase of the stability constants by a factor of $10^{2.42}$ with respect to 1. Furthermore, the $Be^{2+}$-3 interactions are demonstrated by $^1H$ NMR experiments in highly polar solvent medium, DMSO-$d_6$. Higher selectivities were also observed for $Be^{2+}$ when the ditopic receptor, 3 was incorporated into PVC membranes and tested as ion selective electrodes at neutral pH.