Reactivity and molecular modeling of new solvatochromic mixed-ligand copper(II) chelates of 2-acetylbutyrolactone and dinitrogen bases

• Solvatochromic Cu(II)-chelates.
• Mononuclear mixed ligand chelates.
• Specific and non-specific solvent interactions with metal chelates.
• Molecular modeling of free ligands and their chelates has been calculated.

A new series of solvatochromic mononuclear mixed ligand chelates with the general formula: Cu(AcBL)(L)X; where AcBL = 2-acetylbutyrolactonate, L = N,N,N′,N′-tetramethylethylenediamine (Me4en), N,N,N′,N′-tetramethylpropylene diamine (Me4pn), 1,10-phenanthroline (Phen) or 2,2′-bipyridyl (Bipy) and X = ClO4−, NO3− or Br− have been synthesized and characterized by the analytical and spectral methods, as well as magnetic and molar conductance measurements. The d–d absorption bands of Me4en-chelates as Nujol mulls or weak donor solvents solutions revealed square-planar, distorted octahedral and/or distorted trigonal bipyramid geometries for the perchlorate, nitrate and bromide chelates, respectively. However, an octahedral structure is identified for chelates in strong donor solvents. Perchlorate chelates show a remarkable color change from violet to green as the Lewis basicity of the donor solvent increases, whereas bromide chelates are mainly affected by the Lewis acidity of solvent. Specific and non-specific interactions of solvent molecules with the chelates were investigated on the basis of unified solvation model. Structural parameters of the free ligands and their Cu(II)-chelates have been calculated on the basis of semiempirical PM3 level and correlated with the experimental data.

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