THERMOCHEMICAL DISSOLUTION ENTHALPY OF METALLOPORPHYRINS IN ANHYDROUS SOLUTIONS
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The article presents a thermochemical study of the dissolution and solvation of chlorophyll (a), its ligand, and its metal analogues containing Cu(II), Ni(II), Co(II), Zn(II), Cd(II), Fe(III), and Mn(III) in anhydrous organic solvents of different chemical nature. Calorimetric measurements were carried out at 298.15 K in inert aprotic solvents, including CCl₄, C₆H₆, and C₆H₅NO₂, the proton-donor solvent CHCl₃, and proton-acceptor solvents such as DMF, pyridine, and piperidine. Standard dissolution enthalpies of the investigated compounds were determined. The experimental results showed that, within the investigated concentration range, the dissolution enthalpy is essentially independent of porphyrin concentration. Benzene was used as a reference solvent to calculate transfer enthalpies to other solvents. Metal complex formation was found to affect both the crystal-lattice energetics and solvation behavior of the porphyrin macrocycles. Chloroform exhibited particularly strong solvating ability toward chlorophyll ligands and their metal complexes, which was attributed to hydrogen bonding and specific solute–solvent interactions. The obtained data provide a basis for identifying the main thermodynamic regularities governing the solvation of metalloporphyrins in solvents with different donor–acceptor properties.
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