Structural Variations in the Complete Series of Lanthanoid Complexes of a Calix[4]arene Trisamide

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Lanthanoid picrate (pic) complexes of 5,11,17,23-tetra-tert-butyl-25-hydroxy-26,27,28-tris(diethylcarbamoylmethoxy)calix[4]arene (LH) have been synthesised and structurally characterised, to complete this series for all lanthanoids (other than promethium). From cerium to lutetium, three structural types are observed: Type I, [Ln(L)(O,O′-pic)](pic), Ln=Ce–Dy; Type II, [Ln(L)(O-pic)](pic), Ln=Tb, Ho; Type III, [Ln(L)(HOEt)](pic)2, Ln=Er–Lu. With lanthanum, three different ten-coordinate complexes were characterised; [Ln(L)(O,O′-pic)(HOEt)](pic), [Ln(L)(O,O′-pic)(OH2)](pic), and [Ln(L)(O,O′-pic)(HOMe)](pic). The crystallisation of Type I and II observed for terbium shows that the stability of the different structures are sensitively poised at the transition points. Nevertheless, the structures show that the vacant space in the coordination sphere left by the trisamide L tends to reduce across the series as expected. It is occupied by a bidentate picrate anion and unidentate solvent molecule with lanthanum, a bidentate picrate anion for cerium to dysprosium (Type I), a unidentate picrate anion for terbium and holmium (Type II), and finally a unidentate solvent molecule from erbium to lutetium (Type III). The coordination number thus reduces from 10 to 8 across the series.