Systematic Evaluation of Molecular Recognition Phenomena. 3. Selective Diphosphate Binding to Isomeric Hexaazamacrocyclic Ligands Containing Xylylic Spacers

This is the authors' abstract. We don't add key points for this paper.

The crystal structure of 3,7,11,18,22,26-hexaazatricyclo[26.2.2.2(13,16)]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 equilibrium 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[27.3.1.1(13,17)]tetratriaconta-1(33),13, 15,17(34),29,31-hexaene (Bn) ligand. For the H6P3Pp(2+) those bonding interactions reach a maximum yielding a log KR6 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.