The solvation and redox behavior of mixed ligand copper(II) complexes of acetylacetonate and aromatic diimines in ionic liquids

• Cu(acac)(bipy)Cl and [Cu(acac)(phen)]Cl were studied in ionic liquids (Ils).
• These are reduced in ILs at more negative potentials than in organic solvents.
• EPR shows lower Az and higher gz values for the complexes in ionic liquids.
• Spectroscopic and electrochemical data suggests coordination of the IL anion.

The behavior of two cationic copper complexes of acetylacetonate and 2,2′-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF4 and bmimNTf2 ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower Az and higher gz   values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)2-, MeSO4- and Me2PO4-, which agrees with previous determinations.

The behavior of two cationic copper complexes of acetylacetonate and 2,2′-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl and [Cu(acac)(phen)]Cl, in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes are electrochemically reduced in these ionic media, at more negative potentials than when using organic solvents, which is in agreement with the EPR characterization that showed lower Az and higher gz values for the complexes dissolved in ionic liquids.Figure optionsDownload as PowerPoint slide