Synthesis, characterization, and single crystal X-ray structures of [CoIII(acacen)(thioacetamide)2]ClO4 and [CoIII((BA)2en)(thioacetamide)2]PF6 - Solvatochromic properties of [CoIII(acacen)(thioacetamide)2]ClO4
Journal article, 2005
The trans-[CoIII(acacen)(ta)2]ClO4 (1) and trans-[CoIII((BA)2en)(ta)2]PF6 (2) complexes, where H2acacen = bis(acetylacetone)ethylenediimine, H2(BA))2en = bis(benzoylacetone)ethylenediimine, and ta = thioacetamide, have been synthesized by a solid-state method, and characterized by elemental analyses, IR, UV-vis, and 1H NMR spectroscopy. The crystal and molecular structures of 1 and 2 were determined by X-ray crystallography. Both compounds crystallize in the monoclinic space group P2/n. The ClO4 and PF6 ions are both disordered, ClO4 on a twofold axis in 1 and PF6 on an inversion center in 2. Also bridging N-CH2-CH2-N is disordered in both compounds. The octahedral coordination of Co(III) is slightly distorted in both cases. The thioacetamide ligands are S-bonded and occupy the axial position. The IR, UV-vis, and 1H NMR spectra of the two complexes and their solvatochromic properties are also discussed. The longest wavelength absorption that appears at 517 nm for 1 and at 528 nm for 2 in chloroform is solvent dependent, and is assigned as a metal-mediated ligand-to-ligand charge transfer (LLCT).
Co(III) (Schiff base)