Relative basicities of the oxygen atoms of the Linquist polyoxometalate [Mo_6O_(19)]~(2-) and their recognition by hydroxyl groups in radical cation salts based on functionalized tetrathiafulvalene #pi# donors

摘要

Electrocrystallization of three hydroxylated donor molecules derived from tetrathiafulvalene (TTF) or ethylene-dithiotetrathiafulvalene (EDT-TTF), i.e.Me_3TTF-CH_2OH, EDT-TTF(CH_2OH)_2 and TTF(CH_2OH)_4, in the presence of [n-Bu_4N~+]_2[Mo_6O_(19)]~(2-) afforded 2:1 cation radical salts, [donor~(+ centre dot)]_2[Mo_6O_(19)]~(2-), whose crystal structures have been solved by X-ray diffraction. In the three different salts complex hydrogen bond networks develop in the solid state where the oxygen atoms of both the hydroxyl groups and the [Mo_6O_(19)]~(2-) anions act as hydrogen bond acceptors. The observed hydrogen bonding directed toward one surface, bridging oxygen atom of [Mo_6O_(19)]~(2-) is rationalized by an analysis of ab initio calculations of the distribution of electrostatic potentials.