Spectroscopic evidence on improvement in complex formation of O2N2 aza-crown macrocyclic ligands with Cu(II) acetate upon incorporation with [60]Fullerene

• UV–vis-NIR spectra of the Cu(II) complex of the aza-crowns anchored to C60 (Ln) was measured.
• The spectra displayed a new strong LMCT bands.
• The Kb values of L1 and L2 with Cu(II) were measured
• DFT calculations recommended significant HOMO's alternation for L1 < L2 order.
• Entropic factors are dominant for coordination of Cu(II) with L1 and L2.

The present paper reports the spectroscopic investigations on the complexation of Cu(II) with two macrocyclic ligands bonded to [60]Fullerene (L1 and L2) measured in N-methylpyrrolidone (NMP) as solvent. On the basis of UV–vis-NIR spectroscopy applying Jobs method of continuous variation, typical 1:1 stoichiometries were established for the complexes of Cu(II) with L1, and L2. DFT calculations suggested that superior HOMO distributions spread over the nitrogen-donor (as well as somehow oxygen- donor in L2) groups of L1 and L2 macrocycles were the key factor for the observed Kb value enhancement. Thermodynamic stabilities for these complexes have also been determined employing Benesi-Hildebrand equation and the results were compared in terms of their calculated binding constants (Kb). These measurements showed that L1 and L2 bound to these cations stronger than their parent free macrocyclic ligands 1 and 2, respectively. Furthermore, Kb values found for L2 complexes revealed that it could coordinate Cu(II) cation better than L1. Thermodynamic parameters (ΔG, ∆ H, and − ΔS) derived from Van't Hoff equation showed that L1 and L2 coordination of Cu(II) cation were occurred due to both enthalpic and entropic factors while the coordination of Cu(II) with their parent macrocyclic ligands 1 and 2 only enjoyed from only enthalpic advantages.

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