EXCESS PROTON HYDRATE STRUCTURES WITH LARGE PROTON POLARIZABILITY IN THE CHANNEL OF TRIOXAALKYL PHOSPHATE

Complexes of tributyl phosphate (TBPO) and tris(10-chloro-3,6,9-trioxa decyl) phosphate (TODPO) with HAuCl4 and their hydrates with various a mounts of water were studied by FT-IR spectroscopy. TBPO with HAuCl4 f orms homoconjugated PO+H ... OP reversible arrow PO ... H+OP hydrogen bonds with large proton polarizability. In hydrates of homoconjugated PO+H ... OP reversible arrow PO ... H+OP complexes, H5O2+ is formed wi th a hydrogen bond having large proton polarizability. In the 1:1 mixt ure no H3O+, but both H5O2+ and PO+H ... OP reversible arrow PO ... HOP homoconjugated bonds are present in the a 1.1 ratio. In the protona ted and hydrated mixtures of TODPO no homoconjugated PO+H ... OP rever sible arrow PO ... H+OP hydrogen bonds and no H5O2+ species are found. In these complexes the proton and water molecules are present in the channels which show large proton polarizability. The behaviour of thes e protonated and hydrated channels is discussed with respect to the be haviour of the gramicidin channel.