Novel Co^III complexes containing fluorescent coumarin-N-acylhydrazone hybrid ligands: Synthesis, crystal structures,...

A series of new Co^III complexes of the type [Co(dien)(L1-L3)]ClO₄ (1-3), containing fluorescent coumarin-N-acylhydrazonate hybrid ligands, (E)-N'-(1-(7-oxido-2-oxo-2H-chromen-3-yl)ethylidene)-4-R-benzohydrazonate [where R=H (L1^2-), OCH₃ (L2^2-) or Cl (L3^2-)], were obtained and isolated in the low spin Co^III configuration. Single-crystal X-ray diffraction showed that the coumarin-N-acylhydrazones act as tridentate ligands in their deprotonated form (L^2-). The cation (+1) complexes contain a diethylenetriamine (dien) as auxiliary ligand and their structures were calculated by DFT studies which were also performed for the Co^II (S=1/2 and S=3/2) configurations. The LS Co^II (S=1/2) concentrated the spin density on the O-Co-O axis while the HS Co^II (S=3/2) exhibited a broad spin density distribution around the metallic center. Cyclic voltammetry studies showed that structural modifications made in the L^2- ligands caused a slight influence on the electronic density of the metal center, and the E_1/2 values for the Co^III/Co^II redox couple increased following the electronic effect of the R-substituent, in the order: 2 (R=OCH₃)<1 (R=H)<3 (R=Cl). The theoretical redox potentials (E°) of the process Co^III→Co^II were calculated for both Co^II spin states (S=1/2 and S=3/2) and a better correlation was found for Co^III→Co^II (S=1/2), compared with experimental values vs SHE (E^°_calc=-0.37, -0.36 and -0.32V vs E^°_exp.=-0.371, -0.406 and -0.358V, for 1-3 respectively). Complexes 1-3 exhibited a very intense absorption band around 470nm, assigned by DFT calculations as π-π* transitions from the delocalized coumarin-N-acylhydrazone system. 1-3 were very stable in MeOH for several days. Likewise, 1-3 were stable in phosphate buffer containing sodium ascorbate after 15h, which was attributed to the high chelate effect and σ-donor ability of the L^2- and dien ligands.