The influence of cation complexation in NaClO3 and KClO3 by crown ethers on the electronic structure of salts studied by 35Cl‐N.Q.R. method

Abstract

AbstractMe⊕ (Me = Na; K) cations in MeClO3 chlorates were complexed by crown ethers (CE): 12C4, 15C5 and 18C6 in solution. In the solid phase we could obtain only Na(15C5)ClO3 and K(18C6)ClO3 complexes significant shift in 35Cl‐n.q.r. frequency with respect to the frequency of pure sodium and potassium chlorates was observed. The shifts at 77K were –2.879 MHz for Na(15C5)ClO3 and –1.004 for K (18C6)ClO3.For other reaction mixtures the 35Cl‐n.q.r. frequencies observed were the same as for the appropriate pure chlorates which confirmed that the expected complexation in the solid phase had not occurred. The investigation described in this paper proved a rapid increase in selectivity of crown ethers at the transition from the solution to the solid state. Moreover, in the solid phase of Me(CE)ClO3 complexes a significant increase was found in the shielding effect of the Me⊕ cation by the surrounding crown ether.