Spectroscopic Study of the Hydration Equilibria and Water Exchange Dynamics of Lanthanide (III) Complexes of 1, 7-Bis (carboxymethyl)-1, 4, 7, 10-tetraazacyclododecane (DO2A)

摘要

The hydration state of a series of [Ln(DO2A)(H_2O)_N]~+ complexes in aqueous solution at pH = 6.4-7.0 was studied by measuring the lanthanide-induced ~(17)O shifts (LIS) of water [Ln includes elements from Ce to Yb; DO2A = 1,7-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane]. Their contact contribution, obtained from Reilley plots, indicated a decrease in the inner-sphere water coordination number of the [Ln(DO2A)(H_2O)_n]~+ complexes from n = 3 (Ce-Eu), to n = 2 (Tb-Yb). A temperature-dependent UV/Vis absorption study of the 578-582 nm ~7F_0 → ~5D_0 transition band of [Eu(DO2A)(H_2O)_n]~+ in aqueous solution showed that this complex is present in an equilibrium between eight- and nine-coordinate species species with n = 2 and n = 3, respectively. The hydration equilibrium parameters (2 <-> 3), K_(2-3)~(289) = 4.0 ± 0.2, ΔH_(2-3)~0 = -12.1 ± kJ mol~(-1) and Δ_(2-3)~0 = -28.9 ± 3 J mol~(-1) K~(-1), correspond to an average hydration number of 2.65 - 2.85 in the temperature range 273-363 K. A variable temperature, multiple field ~(17)O NMR study combined with direct EPR measurements of the transverse electronic relaxation rates has been used to obtain the parameters characterizing water exchange, rotation and electronic relaxation, all influencing the proton relaxivity of [Gd(DO2A)(H_2O)_(2-3)]~+. The small increase in the water exchange rate of [Gd(DO2A)(H_2O)_(2-3)]~+ (k_(ex)~(298) = (10 ± 5) * 10~6 s~(-1)) relative to that of [Gd(DOTA)(H_2O)]~- (4.8 * 10~6 s~(-1) is a consequence of an unfavorable interplay of charge and hydration equilibria. The value of τ_R~(298) = 40 ± 1 ps is short, and the electronic relaxation rate (1/T_(2e) ≈ 1.2 * 10~(10) s~(-1)) is fast relative to [Gd(DOTA)(H_2O)]~- (1.3 - 2.4 * 10~9 s~(-1) for B = 0.34 T). These parameters negate to some extent the expected increase in proton relaxivity of the [Gd(DO2A)(H_2O)_(2-3)]~+ complex.