Phase-dependent polymerization isomerism in the coordination complexes of a flexible bis(β-diketonato) ligand.

First prepared in the late 70s, the pro-ligand 1,3-bis(3,5-dioxo-1-hexyl)benzene (H ₂ bdhb) contains two acetoacetyl terminations linked to a central 1,3-phenylene unit through dimethylene bridges. Since each termination can be either in diketonic or keto-enolic form, in organic solution it exists as a mixture of three spectroscopically resolvable tautomers. In the presence of pyridine, Co ²⁺ and the bdhb ^2- anion form a crystalline dimeric compound with formula [Co ₂ (bdhb) ₂ (py) ₄ ] (2) and a Co⋯Co separation of more than 11 Å. Complex 2 contains two pseudo-octahedrally coordinated and non-interacting high-spin cobalt(II) ions ( S = 3/2) displaying a large easy-plane anisotropy ( D ∼ 70 cm ^-1 ), as consistently indicated by magnetic measurements, X-band EPR spectra, and complete active space self-consistent field/N-electron valence state perturbation theory (CASSCF/NEVPT2) calculations. At cryogenic temperatures ( T < 7 K) and in an applied static magnetic field, the compound shows detectably slow magnetic relaxation, which occurs through direct and Raman mechanisms. Combined mass spectrometry, UV-Vis, and ¹ H/ ² H NMR data, including an isotopic labelling experiment and a determination of molecular weight by diffusion ordered spectroscopy (DOSY), show that 2 rearranges to monomeric high-spin [Co(bdhb)(py) _x ] species ( x = 0, 1, or 2) in organic solution (CH ₂ Cl ₂ , THF) with concomitant partial dissociation of the py ligands. The X-band EPR spectra in a frozen CH ₂ Cl ₂ /toluene matrix concurrently suggest a significant alteration of the coordination environment upon dissolution. These observations are fairly well reproduced by density functional theory (DFT) and CASSCF/NEVPT2 calculations on the lowest Gibbs free energy conformers of each species, as provided by an extensive conformational search based on meta-dynamics simulations and semiempirical tight-binding methods. After the vanadyl analogue, compound 2 provides the second example of polymerization isomerism in the 1 : 1 adducts of bdhb ^2- with divalent metal ions.