Conversion of lanthanide glutarate chlorides with interstitial THF into lanthanide glutarates with unprecedented topologies

Abstract

Abstract Using slow diffusion methods at room temperature (RT), we obtained four isomorphous lanthanide glutarate chlorides, accommodating interstitial THF and water molecules, [Ln2(Glut)2Cl2(H2O)8]·2H2O·THF (1–4), with Ln = La (1), Ce (2), Pr (3), Nd (4). They assemble as 3-dimensional (3D) lanthanide (Ln) coordination polymers with LnO10 coordination polyhedra. Their topology was elucidated to be a 4-coordinated sql net. 1–4 slowly dissolve in water liberating the entrapped THF molecules and reassemble as regular Ln-glutarate hydrates when the solution is deprived of THF and water by slow evaporation. The new products crystallize as [Ln2(Glut)3(H2O)3]·5H2O (5–7), with Ln = La (5), Ce (6), Pr (7), and [Nd2(Glut)3(H2O)2]·3.5H2O (8). 5–7 are isomorphous and crystallize as 3D-networks with two crystallographically independent LnO10 and LnO9 coordination spheres that assemble into Ln2O18 and Ln2O16 polyhedra via edge sharing. Their topology has not previously been observed and was found to be a 3,4,4,5,6-coordinated 3,4,4,5,6T61 net. The known compound 8 crystallizes also as a 3D-network and is isomorphous to other previously described lanthanide glutarate hydrates. 8 has a 3,4,5-coordinated 3,4,5T202 net topology, which has not been determined before.