Linear, Zigzag, and Helical Cerium(III) Coordination Polymers

Five novel one-dimensional cerium(III) carboxylate coordination polymers, [Ce(O2CCH2CHMe2)3(EtOH)2]n (1), {[Ce(O2CCH2Me)3(H2O)]·0.5(4,4′-bpy)}n (2; 4,4′-bpy = 4,4′-bipyridine), {[Ce2(O2CCHMe2)6(H2O)3]}n (3), {[Ce3(O2CCHMe2)9(nPrOH)4]}n (4), and {[Ce3(O2CCHMe2)9(HO2CCHMe2)2(H2O)2]·2Me2CHCO2H}n (5), showcase the surprisingly consistent tendency of Ce(III) coordination network structures to adopt one-dimensional connection modes. The type of carboxylate as well as the reaction solvents determines the exact bridging versus end-on coordination modes for the carboxylates and, in turn, discriminate between linear, zigzag, and helical arrangements. Detailed magnetochemical analyses reveal pronounced single-ion effects and the expected weak antiferromagnetic coupling.