P-tert-Butylthiacalix[4]arenes functionalized by N-(4'-nitrophenyl)acetamide and N,N-diethylacetamide fragments: Synthesis and binding of anionic guests

Abstract

New p-tert-butylthiacalix[4]arenes, which are mono-, 1,2-di- and tetrasubstituted at the lower rim containing N-(4'- nitrophenyl)acetamide and N,N-diethylacetamide groups in cone and partial cone conformations have been synthesized. Their complexation ability towards a number of tetrabutylammonium salts n-Bu4NX (X = F-, Cl-, Br-, I-, CH3CO2 -, H2PO4-, NO3-) was studied by UV spectroscopy. The effective receptor for the anions studied as well as selective receptors for F-, CH3CO2 - and H2PO4- ions, which based on the synthesized thiacalix[4]arenes, have been obtained. It was shown that p-tertbutylthiacalix[ 4]arene tetrasubstituted at the lower rim by N-(4'-nitrophenyl)acetamide moieties bonded to the anions studied with association constants within the range of 3.55 × 103-7.94 × 105 M-1. Besides, the binding selectivity for F-, Cl-, CH3CO2-, and H2PO4-anions against other anions was in the range of 4.1-223.9. Substituting one or two fragments in the macrocycle with N,Ndiethylacetamide groups significantly reduces the complexation ability of the receptor. In contrast to the 1,3-disubstituted macrocycle containing two N-(4'-nitrophenyl)acetamide moieties, the 1,2-disubstituted thiacalix[4]arene, which contains only one such fragment and a N,N-diethylacetamide moiety, selectively binds F- anions.