Spectrophotometric and electrochemical behavior of a novel azocalix[4]arene derivative as a highly selective chromogenic chemosensor for Cr

In this study, a novel azocalix4]arene derivative, 5,11,17-tris(1-naphtyl)azo]-25,26,27,28-tetrahydroxy-calix4]arene (NAC4) bearing napthyl groups on the upper rim was synthesized. Its complexation behavior for alkali, alkaline-earth and various heavy metal ions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺, Hg²⁺, Ni²⁺, Cd²⁺, Cu²⁺, Zn²⁺, Co²⁺, Fe²⁺, Cr³⁺, Ag⁺) was investigated by spectroscopic and voltammetric methods. This chemosensor exhibits decreased absorbance in the presence of Hg²⁺ and a unique absorbance quenching effect only for Cr³⁺. In addition, a new absorption band centered at 565 nm with the formation of the 1:1 host–guest complex (Cr³⁺-NAC4) was observed in the case of Cr³⁺, leading to an obvious color change from light orange to dark lilac. In voltammetric experiments, Cr³⁺ ions decreased voltammetric peaks of NAC4, whereas no significant changes occurred in the presence of the other metal ions. The Benesi–Hildebrand method was used to determine a logarithmic value of 3.76 for the association constant of the complex between Cr³⁺ and NAC4.