SOLUTION AND SOLID-STATE CHARACTERIZATION OF HIGHLY RIGID, 8-COORDINATE LANTHANIDE(III) COMPLEXES OF A MACROCYCLIC TETRABENZYLPHOSPHINATE

The ligand azacyclododecanetetrakis(methylenebenzylphosphinic acid), 1 , forms kinetically stable complexes with lanthanide ions (Ln = Eu, Gd , Tb, Yb, and Y) which are eight-coordinate (no bound water), with sin gle diastereoisomers being preferentially formed (RRRR or SSSS at each stereogenic phosphorus centre). The H-1 NMR spectra for the Eu and Yb complexes have been assigned and no significant fluxional behavior is observed in the temperature range 5-80 degrees C at 400 MHz. The gado linium complex is a promising outer-sphere contrast agent for magnetic resonance imaging, and analyses of variable temperature NMRD profiles suggest that the nearest water molecule is 4.25 Angstrom distant from Gd (cf. 3.82 Angstrom for the P-Me analogue). A relatively strong com plex is formed with bovine serum albumin (K-d = 2.8 x 10(-4) dm(3) mol (-1)) leading to a significantly enhanced relaxivity in which a major contribution may arise from the exchange of mobile protons on the prot ein which undergo rapid dipolar relaxation caused by the proximity of the paramagnetic Gd ion. The crystal structures of the monohydrochlori de salt of the free ligand and of the anionic yttrium(III) complex (as its oxonium salt) are reported. In the structure of the yttrium compl ex there is no metal-bound water molecule, with the nearest water bein g 5.62 Angstrom from the yttrium atom. Crystal data for [(1)H]Cl: mono clinic, C2/c, a = 48.21(3) Angstrom, b = 11.455(4) Angstrom, c = 18.47 4(11) Angstrom, beta = 103.88(4)degrees, V = 9905(9) Angstrom(3), Z = 8,2484 reflections, R = 0.078. Crystal data for H3O[Y(1)]: orthorhombi c, Pbcn, a = 22.332(5) Angstrom, b = 23.052(9) Angstrom, c = 21.301(8) Angstrom, V= 10 965 Angstrom(3), Z = 8, 1625 reflections, R = 0.089.