Deciphering the effect of amine versus imine ligands of copper(II) complexes in 2-aminophenol oxidation.

A series of amine (1-6) and imine (5',6') based copper(II) complexes with tridentate (NNO) ligand donors were synthesized and characterized using modern analytical techniques. All the complexes were subjected to 2-aminophenol (OAP) oxidation to form 2-aminophenoxazin-3-one, as a functional analogue of an enzyme, phenoxazinone synthase. In addition, a critical comparison of the reactivity using the amine-based complexes with their respective imine counterparts was achieved in both experimental as well as theoretical studies. For instance, the kinetic measurement revealed that the imine-based copper(II) complexes (kcat, 2.4 × 105-6.2 × 106 h-1) are better than amine-based (kcat, 6.3 × 104-3.9 × 105 h-1) complexes. The complex-substrate adducts [Cu(L3)(OAP)] (7) and [Cu(L3')(OAP)] (7') were characterized for both systems by mass spectrometry. Further, the DFT study was performed with amine- (3) and imine- (3') based copper(II) complexes, to compare their efficacy in the oxidation of OAP. The mechanistic investigations reveal that the key elementary step to determine the reactivity of 3 and 3' is the proton-coupled electron transfer (PCET) step occurring from the intermediates 7/7'. Further, the computed HOMO-LUMO energy gap of 7' was smaller than 7 by 0.8 eV, which indicates the facile PCET compared to that of 7. Moreover, the coupling of the OAP moiety using imine-complexes (ΔGR.E = -5.8 kcal/mol) was found to be thermodynamically more favorable than amine complexes (ΔGR.E = +3.3 kcal/mol). Overall, the theoretical findings are in good agreement with the experimental results.

Carbazole appended trans-dicationic pyridinium porphyrin finds supremacy in DNA binding/photocleavage over a non-carbazolyl analogue.

A carbazolyl appended trans-pyridyl porphyrin (1) was synthesized and its dicationic form 2 was obtained by methylation of the pyridyl group. Copper and zinc complexes of porphyrin 2 (Cu(II), 3; Zn(II), 4) were isolated and characterized by various modern spectroscopic techniques. The DNA binding properties of 2, 3, and 4 have been explored against calf thymus-DNA (CT-DNA). DNA binding was quantized using the intrinsic binding constant (Kb) that was calculated by UV-visible absorption spectroscopy, and the value Kb = 1.6 × 106 M-1 for compound 2 reveals a better interaction of 2 towards CT-DNA than those of 3 (3.1 × 105 M-1) and 4 (3.4 × 105 M-1), which follows the order 2 > 4 > 3. The fluorescence quenching efficiency and ethidium bromide quenching assay also indicated a good binding affinity of all the compounds towards CT-DNA. Furthermore, the spectroscopic data suggest that the possible mode of interaction is intercalation. The docking studies were in accordance with the experimental results. Notably, DNA cleavage studies reveal that 2 shows better damage than 3 and 4 which is in accordance with the binding affinity order 2 > 4 > 3. The observed quantum yield (2: 0.65, 3: 0.33, and 4: 0.97) and no change in DNA cleavage in the presence of NaN3 reveal the involvement of singlet oxygen. The singlet excited state lifetimes were in the range of 6.3-1.2 ns. Furthermore, these porphyrins can be investigated as interesting photosensitizers in photodynamic therapy and photochemotherapy.