The crystal structure of 3,7,11,18,22,26-hexaazatricyclo[18.104.22.168 23,16]tetratriaconta-1 (31),13(34),14,16(33),28(32),-29-hexaene hexahydrobromide salt [(H6P3)Br6] has been determined by means of X-ray diffraction analysis. It crystallizes with an additional molecule of ethanol and half a molecule of water per molecule of the hydrobromide P3 ligand. The protonation constants of P3 and its host-guest interactions with monophospate (Ph) and pyrophosphate (Pp) have been investigated by potentiometric equilibrum methods. Ternary complexes are formed in aqueous solution as a result of hydrogen bond formation and Coulombic interactions between the host and the guest; formation constants for all the species obtained are reported and compared with the isomeric 3,7,11,19,23,27-hexaazatricyclo[22.214.171.124,17]tetratriaconta-1 (33), 13(33),13, 15,17(34),29,31-hexaene (Bn) ligand. For the H6P3Pp 2+ those bonding interactions reach a maximum yielding a log K R6 of 5.87. The selectivity of the P3 ligand with regard to the monophosphate and pyrophosphate substrates (S) is discussed and illustrated with global species distribution diagrams showing a strong preference for the latter over the former as a consequence of the much stronger formation constants with pyrophosphate. An analysis of the isomeric effect is also carried out by comparing the P3-S versus Bn-S systems. In the best case, a selectivity of over 88% is achieved for the diphosphate complexation when using the meta isomer over the para, due solely to the size and shape of the receptors cavity.
|Publication status||Published - 15 Dec 2003|