Dinuclear copper and zinc complexes of a hexaazamacrocycle containing p-xylyl spacers and bridging anions: theoretical and spectroscopic studies

The hexaazamacrocycle 7,22-dimethyl-3,7,11,18,22,26-hexaazatricyclo[26.2.2.213,16]tetratriaconta-1(30),13,15,28,31,33-hexaene (Me2[30]pbz2N6) was synthesized and characterised by single crystal X-ray diffraction. The macrocycle adopts a conformation with the two aromatic rings almost parallel at a distance of ca. 4.24 (angstrom), but displaced relative to each other by ca. 1.51 (angstrom). The protonation constants of this compound and the stability constants of its complexes with Cu2+ and Zn2+, were determined in watermethanol (9 : 1 v/v) at 25 °C with ionic strength 0.10 mol dm^-3 in KCl. The potentiometric and spectroscopic studies (NMR of zinc, cadmium and lead complexes, and EPR of the copper complexes) indicate the formation of only dinuclear complexes. The association constants of the dinuclear copper complex with anions (thiocyanate, terephthalate and glyphosate) and neutral molecules (1,4benzenedimethanol, p-xylylenediamine and terephthalic acid) were determined at 20 °C in methanol. The structural preferences of this ligand and of its dinuclear copper(II) complex with a variety of bridging ligands were evaluated theoretically by molecular mechanics calculations (MM) and molecular dynamics (MD) using quenching techniques.