ANION CRYPTATES - SYNTHESIS, CRYSTAL-STRUCTURES, AND COMPLEXATION CONSTANTS OF FLUORIDE AND CHLORIDE INCLUSION COMPLEXES OF POLYAMMONIUM MACROBICYCLIC LIGANDS

Three macrobicyclic octamines 1-3 and the macrotricyclic hexadecamine 14 have been synthesized. The octamines 1-3 bind anionic substrates wh en protonated. The stability constants of the complexes between the pr otonated forms of the macrobicyclic polyamines and halide anions have been determined by pH-metric measurements. The stability constants in H2O are very high; 1 in its hexaprotonated form binds F- with high sel ectivity (selectivity F-/Cl- > 10(8)), while 3 exhibits strong stabili ty constants for both F- and Cl-. Three X-ray structures have been obt ained, one where F- is held inside the cavity of 1.6H(+), one where Cl - is included in 3.6H(+), and 3.6H(+) where the cavity is empty.