Raman spectroscopic study of the conformational change of 12-crown-4 due to cation capture

Raman spectra of the Li⁺, Na⁺, K⁺, NH⁺₄, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺ complexes of 12-crown-4 and also 12-crown-4 in various states are observed. The spectra of 12-crown-4 change remarkably by complex formation with cations. Normal vibration calculations of various conformations of 12-crown-4 are carried out. On the basis of the observed spectra and the results of the calculations, the conformation of 12-crown-4 in the Li⁺, Na⁺, K⁺, NH⁺₄, Mg²⁺ complexes is found to have approximate D_2d symmetry, while that in the Ca²⁺, Sr²⁺, Ba²⁺ complexes is found to have approximate C_2V symmetry.