Lower Rim 1,3-Di{4-antipyrine}amide Conjugate of Calix[4]arene: Synthesis, Characterization, and Selective Recognition of Hg2+ and Its Sensitivity toward Pyrimidine Bases

The structurally characterized lower rim 1,3-di{4-antipyrine}amide conjugate of calix[4]arene (L) exhibits high selectivity toward Hg2+ among other biologically important metal ions, viz., Na+, K+, Ca2+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Zn2+, Cd2+, Hg2+, Pb2+, and Ag+ as studied by fluorescence, absorption, and ES1 MS. L acts as a sensor for Hg2+ by switch-off fluorescence and exhibits a lowest detectable concentration of 1.87 +/- 0.1 ppm. The complex formed between L and Hg2+ is found to be 1:1 on the basis of absorption and fluorescence titrations and was confirmed by ESI MS. The coordination features of the mercury complex of L were derived on the basis of DFT computations and found that the Hg2+ is bound through an N2O2 extending from both the arms to result in a distorted octahedral geometry with two vacant sites. The nanostructural features such as shape and size obtained using AFM and TEM distinguishes L from its Hg2+ complex and were different from those of the simple mercuric perchlorate. L is also suited to sense pyrimidine bases by fluorescence quenching with a minimum detection limit of 1.15 +/- 0.1 ppm in the case of cytosine. The nature of interaction of pyrimidine bases with L has been further studied by DFT computational calculations and found to have interactions through a hydrogen bonding and NH-pi interaction between the host and the guest.