P–C Bond Cleavage-Assisted Lanthanide Phosphate Coordination Polymers

The reaction of lanthanide(III) salts with an organodiphosphonic acid under hydrothermal conditions resulted in a P-C bond cleavage affording [{Eu-4(PO4)(PO4)(0.5)x(4)(PO4)(0.25x4)(H2O)(2)}center dot 6H(2)O](n) (1), [{Dy-4(PO4)center dot(PO4)(0.5x4)(PO4)(0.25x4)(H2O)(2)}center dot 6H(2)O](n) (2), and [{Gd(PO4)(0.5)(PO4)(0.5)(H2O)(3)}center dot 2H(2)O](n) (3). 1 and 2 are porous 3D coordination polymers whose repeating units possess a dimeric motif. While one lanthanide ion in the dimer is eight-coordinate in a distorted square-antiprismatic geometry, the other is nine-coordinate and present in a distorted monocapped square-antiprismatic geometry. In contrast to 1 and 2, 3 possesses a 2D architecture; the asymmetric unit contains a monomeric Gd-III center which is nine-coordinate in a distorted monocapped square-antiprismatic geometry.