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Structural diversity in the series of lanthanide complexes [Ln(Ph<sub>3</sub>PO)<sub>n</sub>(NCS)<sub>3</sub>] (n = 3, 4)

OAI: oai:purehost.bath.ac.uk:openaire_cris_publications/c93a5a5a-8fb4-4216-b99e-f4f385a37d21 • DOI: https://doi.org/10.1016/j.poly.2022.115826
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Abstract

Two unique series of lanthanide complexes [Ln(Ph3PO)4(NCS)3] (Ln = La-Tb, except Pm) and [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) have been structurally characterised. The isomorphous series [Ln(Ph3PO)4(NCS)3] crystallises in the monoclinic centrosymmetric space group P21/c, and the metals display a capped octahedral coordination geometry. In contrast, the isomorphous series [Ln(Ph3PO)3(NCS)3] (Ln = Sm-Lu, Y) crystallise in the non-centrosymmetric space group R3, with the metal displaying an octahedral coordination geometry; the fac-isomer being observed in all cases. Intriguingly, for the metals Sm-Tb both the seven and six coordinate complexes can be isolated from the respective synthetic routes suggesting a structural equilibrium in solution. An analysis of the distortions of the ligand polyhedron in the two series using the continuous shape measurement (CShMs) method suggests trends across the series relating to the fit of the ligands with the size of the lanthanide ions.