Structure Directing Effects of the Tetraphenylphosphonium Cation upon the Formation of Lanthanoid Anilate Coordination Polymers

Four lanthanoid anilate coordination polymers (CPs) were synthesised using fluoranilate and chloranilate ligands with La(III), Eu(III) and Dy(III), and PPh₄⁺ as the countercation. The presence of the PPh₄⁺ countercation had a structure directing effect on the CP topology, with a 3D diamondoid (dia) network obtained with La(III) whilst 2D square grid (sql) networks were obtained with Eu(III) and Dy(III). This work represents the first use of fluoranilate in lanthanoid anilate CPs. The additional hydrogen bonding sites afforded by the fluorine substituent influences the packing of the crystal structure whilst the variation in lanthanoid ion size helps determine the topology of the CP.