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Reaction of the pseudotetrahedral tetracarboxylic acidproligandtetrakis(4-carboxyphenyl)silane (H4L) with salts of variouslanthanoid metals has afforded three new lanthanoid coordination polymers:{[H3O]2[Ce2(L)2(H2O)2]·2DMF·2H2O}∞(1), {[Eu3L2(NO3)(DMF)4(H2O)]·0.5DMF·6H2O}∞(2), and {Eu(HL)(DMF)2(H2O)]·DMF·2.5H2O}∞(3) (DMF = N,N′-dimethylformamide), which have been structurallycharacterized by single-crystal X-ray diffraction. Compounds 1and 2are both noninterpenetrated three-dimensionalnetworks that display the rare fluorite (CaF2) topology.In compound 1, the fully deprotonated L4–ligands act as pseudotetrahedral 4-connecting nodes and dinuclearcerium-carboxylate building blocks act as 8-connecting nodes, whilein compound 2the L4–ligands and trinucleareuropium-carboxylate units are 4- and 8-connecting, respectively.In contrast, compound 3exhibits a two-dimensional layeredstructure with triply deprotonated HL3–ligandsacting as 3-connecting units, linking single europium centers withineach layer. Gas sorption studies of 2show a high affinityof the pretreated microcrystalline solid for carbon dioxide gas. [ABSTRACT FROM AUTHOR]