Lanthanide(III) (Er/Ho) coordination polymers for a photocatalytic CO2 cycloaddition reaction.

Two new isostructural carboxylate-bridged lanthanide ribbons having the chemical formula [Ln2(4-ABA)6]n [4-ABA = 4-aminobenzoate, Ln: holmium (Ho) and erbium (Er)] were synthesized by a solvothermal method and fully characterized using multiple analytical, spectroscopic, and computational techniques. Single-crystal X-ray diffraction analysis reveals that both lanthanide coordination polymers (Ln-CPs) exhibit linear ribbon-like structures built up by dinuclear Ln2(4-ABA)6 units and bridged by carboxylate groups. Ln-CPs showed remarkably high thermal and chemical stabilities. Ho-CP and Er-CP exhibited similar band gaps of 3.21 eV and 3.22 eV, respectively, showing their photocatalytic ability under UV light. The photocatalytic activities of Ln-CPs were examined in the CO2 cycloaddition of epoxides to cyclic carbonates under solvent-free conditions, and full conversion (yields up to 99.9%) to the product was achieved. Ln-CP photocatalysts retained the same product yields over five consecutive cycles. Additionally, the experimental magnetic studies indicated that both Ln-CP crystals are antiferromagnetic at low T, which is confirmed by density functional theory calculations.