Synthesis of calix[4]arene(amido)monocrowns and their photoresponsive derivatives

A series of new calix[4]arene(amido)mono-crown compounds have been synthesized through aminolysis of calix[4]arene esters and intramolecular cyclization of the intermediates. The title compounds were converted into their nitro and azo substituted derivatives to provide novel photoresponsive molecular receptors for transition metal ions. Single crystal X-ray analysis of calix[4]arene(ethyleneamido)mono-crown (2a) revealed that the compound is present in a cone conformation with an amido loop that caps the lower rim of calix[4]arene cavity to result,in stacking along axis a and axis c to provide supramolecular aggregates in the solid state. Evaluation of synthesized macrocycles in the solution phase for recognition of transition metal cations (Cr3+, Fe2+, Co2+, Ni2+, Cu2+, Ag+, Cd2+, Ph2+, Hg+, Hg2+, Pd2+, and pt(2+)) by UV-visible spectroscopy revealed that p-tert-butyl-calix[4]arene mono-(amidocrown) 1c selectively shows a blue shift at 38 nm on interaction with Hg+ ions. (c) 2006 Elsevier Ltd. All rights reserved.