Complexation properties of macrocyclic polyoxadiazadiphosphonates

The macrocycle 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-diyldimethylenediphosphonic acid (H(4)L(1)), its bis(ethyl ester) (H(2)L(3)) and 1,4,10-trioxa-7,13-diazacyclopentadecane-7,13-diyldimethylenediphosphonic acid (H(4)L(5)) were prepared. The protonation constants of the macrocycles and the stability constants of their complexes with alkaline-earth-metal ions, lanthanide ions, Zn2+, Cd2+ and Pb2+ were determined by pH-potentiometric titration. The phosphonate (L(3))(2-) forms only unprotonated complexes ML, while (L(1))(4-) and (L(5))(4-) form ML, monoprotonated complexes, M(HL), and diprotonated complexes, M(H(2)L). The trends in the stability constants through the lanthanide series are similar for all complexes: a weak maximum in log K is observed at around Pr3+, Nd3+ and a minimum at about Tb3+, Ho3+. The chemical shifts of the non-labile protons of L(1) indicate that on protonation the first two protons are attached to the two nitrogens, the next two at one of the oxygen atoms of each phosphonate group. The equilibrium data and H-1 NMR spectra of the complexes [LaL(1)](-) and [LuL(1)](-) indicate the increasing role of the metal-phosphonate group interaction in the complexation through the lanthanide series from La3+ to Lu3+. Attachment of the strongly co-ordinating phosphonate groups to the 15- and 18-membered ring macrocycles results in cessation of the size-match selectivity.