Raman spectra and conformations of dibenzo- and dicyclohexano-18-crown-6

Abstract

Conformations of dibenzo-18-crown-6 (DBC), dicyclohexano-18-crown-6 (DCC) and their alkali cation complexes in the solid state and in solution have been investigated by Raman spectroscopy. The Raman spectra were analysed by using the relationships between Raman frequencies and conformations previously found for unsubstituted crown ethers. DBC takes a conformation, ( tCttGttG′t) 2, with gauche ( G) or gauche' ( G′) 2CH 2 bonds, trans ( t) CO bonds and cis ( C) OCCO linkages at the benzene rings, when it complexes with a cation in the solid state and in solution. Uncomplexed DBC adopts another conformation in the solid state, which contains both the trans and gauche conformations about the CH 2CH 2 and CO bonds. In solution, uncomplexed DBC exists as a mixture of conformers including the two conformers described above. Vibrational couplings between the oxyethylene and cyclohexane rings are strong in DCC and its strength depends on the crown conformation. The cation-bound crown rings of DCC isomers A and B in solution predominantly take the same conformation, ( tG′ ttGt) 3, found for the crystalline isomer B-NaBr complex. A metastable conformer containing trans CH 2CH 2 bonding is found for the Na + complexes of both isomers in solution. Uncomplexed DCC adopts different crown ring conformations in isomers A and B in the solid state and diverse conformational states in solution.