Lower rim 1,3-di-amide-derivative of calix[4]arene possessing bis-[N-(2,2 '-dipyridylamide)} pendants: a dual fluorescence sensor for Zn2+ and Ni2+

Abstract

Single crystal XRD structure of the lower rim 1,3-di-amide-derivative of calix[4]arene possessing bis-{N(2,2 '-dipyridylamide)} pendants (L) exhibit two distinct binding cores, viz., N-4 and O-6. L was found to be selective for Zn2+ by switch-on and for Ni2+ by switch-off fluorescence by forming 1: 1 complexes. The binding and the composition of the complex formed have been addressed based on steady state and time-resolved fluorescence spectroscopy in addition to the absorption and ESI MS. As L can detect Zn2+ and Ni2+ to a concentration as low as 142 and 203 ppb, respectively, L can be a very sensitive molecular probe for these ions. The coordination details of the metal ion-bound complexes have been addressed based on ab initio calculations showing that the stabilization energies are commensurate with the coordination formed. (C) 2008