[M^III₂M^II₃]ⁿ⁺ trigonal bipyramidal cages based on diamagnetic and paramagnetic metalloligands

A family of [M^III₂M^II₃]ⁿ⁺ trigonal bipyramidal cages are characterised in the solution and solid state. A family of five [M^III₂M^II₃]ⁿ⁺ trigonal bipyramidal cages (M^III = Fe, Cr and Al; M^II = Co, Zn and Pd; n = 0 for 1–3 and n = 6 for 4–5) of formulae [Fe₂Co₃L₆Cl₆] (1), [Fe₂Zn₃L₆Br₆] (2), [Cr₂Zn₃L₆Br₆] (3), [Cr₂Pd₃L₆(dppp)₃](OTf)₆ (4) and [Al₂Pd₃L₆(dppp)₃](OTf)6 (5) (where HL is 1-(4-pyridyl)butane-1,3-dione and dppp is 1,3-bis(diphenylphosphino)propane) are reported. Neutral cages 1–3 were synthesised using the tritopic [M^IIIL₃ ] metalloligand in combination with the salts Co^IICl₂ and Zn^IIBr₂ which both act as tetrahedral linkers. The assembly of the cis -protected [Pd^II(dppp)(OTf)₂] with [M^IIIL₃ ] afforded the anionic cages 4–5 of general formula [M^III₂Pd^II₃](OTf)₆ . The metallic skeleton of all cages describes a trigonal bipyramid with the M^III ions occupying the two axial sites and the M^II ions sitting in the three equatorial positions. Direct current (DC) magnetic susceptibility, magnetisation and heat capacity measurements on 1 reveal weak antiferromagnetic exchange between the Fe^III and Co^II ions. EPR spectroscopy demonstrates that the distortion imposed on the {MO₆} coordination sphere of [M^IIIL₃] by complexation in the M^III₂M^II₃ supramolecules results in a small, but measurable, increase of the zero field splitting at M^III . Complete active space self-consistent field (CASSCF) calculations on the three unique Co^II sites of 1 suggest D_Co ≈ −14 cm⁻¹ and E/D ≈ 0.1, consistent with the magnetothermal and spectroscopic data.