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. The use of PPh4+ as a countercation template enables the synthesis of La(III) fluoranilate and chloranilate coordination polymers with diamondoid nets, whilst the use of Eu(III) and Dy(III) yields the formation of 2D square grid structures where the PPh4+ counterion is located between the 2D layers. image