Tautocrowns: a concept for a sensing molecule with an active side-arm

A new sensing molecule containing aza-15-crown-5 as a receptor and 4-(phenyldiazenyl)naphthalen-1-ol as a signal converter has been synthesized. In the free ligand, the hydrogen bonding between the tautomeric OH group and the nitrogen atom from the macrocycle fully shifts the tautomeric equilibrium towards the enol form. The complexation reverses the equilibrium as a result of the strong interaction between the metal ion captured in the macrocyclic moiety and the tautomeric carbonyl group. The complex formation is accompanied by strong bathochromic (between 60 and 100 nm) and hyperchromic effects on the absorption spectra. Obviously, the tautomeric OH/Cdouble bond; length as m-dashO groups play the role of an active side-arm in the complexation, supporting it via formation of a 3D cavity and giving possibility for ejection of the guest compound under stimuli to shift the tautomeric process back.