Lanthanide induced variability in localised Co II geometries of four triangular L 3 Co 3 II Ln III complexes.

Four tetranuclear heterobimetallic triangle complexes [L 3 Co 3 Dy(NO 3 ) 2 (H 2 O)(MeOH) 5 ](NO 3 ) (C1), [L 3 Co 3 Gd(NO 3 ) 3 (MeOH) 4 ] (C2), [L 3 Co 3 La(NO 3 ) 2 (H 2 O) 6 ](NO 3 )(H 2 O) (C3), and [L 3 Co 3 TbCl(NO 3 ) 2 (H 2 O) 0.5 (MeOH) 3.5 ] (C4), where H 2 L = 1,4-bisformylnaphthalene-2,3-diol, have been synthesised and structurally characterised. Each complex crystallises with a complete molecule in the asymmetric unit ( Z ' = 1) and displays near perfect octahedrality in two out of three Co II centres. The third Co II ion assumes a different coordination geometry in each complex: six-coordinate octahedral in C1, six-coordinate with a distortion towards trigonal prismatic in C2, five-coordinate trigonal bipyramidal in C3, and five-coordinate square pyramidal in C4; which has been attributed to increasing lanthanide cation size, coupled with a non-macrocyclic coordination environment. Continuous Shape Measurement (CShM) calculations and octahedral distortion parameter calculations were performed, using the SHAPE and OctaDist software packages, respectively, in order to aid in the assessment of each metal centre's local coordination geometry. The preliminary magnetic investigation of C3 found χ m T = 9.4 cm 3 K mol -1 at 300 K and M = 7.1 μ B at 1.8 K, which are approximately two thirds the maximum theoretical values for three Co II ions and indicates the presence of a relatively large zero-field splitting parameter ( D / k B = 65 K) operative in each Co II ion rather than exchange coupling between the Co II centres.