Imidazobenzimidazole fused aza-calix[4]arenes:Synthesis,structure,and Zn^(2+)-selective colorimetric-fluorometric sensor

Tetra(amino)azacalix[4]arene skeleton was functionalized at the bridging NH sites using various aromatic aldehydes via formation of imidazobenzimidazole fused heterocycles.X-ray single crystal analysis revealed distorted 1,3-alternate conformations for the resulting macrocycles.Anthracenyl and pyrenyl modified imidazobenzimidazole fused aza-calix[4]arenes existed as dimers in the solid state,associated mainly through-stacking interactions between the planar polycyclic fluorophores.The tetrapyrenyl modified product was further used as a Zn^(2+)-selective sensor,which showed naked-eye detected color change and enhanced excimer emission.The stoichiometry between the sensor and Zn2+was determined to be 1:1 and the association constant was 1.1×10^(5)L/mol.The sensing process was highly selective and showed strong anti-interference with presence of other cations.The UV-vis spectral changes in the sensing process were completely reversible by alternate addition of Zn^(2+) and F^(-),showing an efficient“on-off-on”result.