Steric control of lanthanide hydration state: fast water exchange at gadolinium in a mono-amide 'DOTA' complex

Detailed analyses of the solution structure and exchange dynamics of two sets of homologous mono-amide triacetate lanthanide complexes (Ln = Eu, Gd) of cyclen have been undertaken. The complex [LnL(1)], bearing an N-linked CH2CH2NHCO-pyridyl moiety, forms mono-aqua (q = 1) species in solution and the Gd complex undergoes rapid water exchange (k(ex) = 11 x 10(7) s(-1), 298 K) as a result of the steric destabilisation of the Ln-water binding interaction. The homologous complex with a C-3 spacing chain, [LnL(2)], forms a q = 0 species.