Molecular Complexation of Arenediazonium Ions by a Calix[4]arene Possessing Two Ester Groups : Molecular Tweezers

: The spectroscopic behaviors of arenediazonium ions in the absence and the presence of a novel calix[4]arene 1 , 3 - alternate conformer possessing two (ethoxycarbonyl) methoxy groups 4 were studied by UV-visible, 1 H NMR, and IR spectra for the first time. 1 , 3 alternate conformer 4 exhibits the large hyposochromic shifts of 85 nm and the binding constants ( K a ) values are greater than 10 4 M -1 , indicating the fact that 4 strongly associates with the diazo group, the interaction being comparable with that with 18-crown-6. However, 4 can not inhibit the dediazoniation of the diazo group indicating the mechanism (A), the macrocyclic effect which sterically inhibits dediazoniation proceeding from the linear Ar-N + ≡ N inserted in the crown ring to the bulky p -intermediate II , is responsible for the stabilization of the diazo group.

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