Copper(II) Inverse‐[9‐Metallacrown‐3] Compounds Accommodating ­Nitrato or Diclofenac Ligands: Structure, Magnetism, and Biological Activity

Autor: Andreas Scorilas, Christos K. Kontos, Alketa Tarushi, Vassilis Psycharis, George Psomas, Vassilis Tangoulis, Dimitris P. Kessissoglou, Catherine P. Raptopoulou
Rok vydání: 2015
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2016:219-231
ISSN: 1099-0682
1434-1948
DOI: 10.1002/ejic.201500769
Popis: Interaction of Cu(NO3)2 with phenyl 2-pyridyl ketoxime (PhPyCNOH) in the presence or absence of sodium diclofenac (Nadicl) leads to the formation of mono- or double-decker trinuclear clusters, respectively, characterized as inverse-9-metallacrown-3 accommodating dicl– or NO3– anions. The structures of [Cu3(PhPyCNO)3(3-O)(NO3)]2 (1) and [Cu3(PhPyCNO)3(3-OH)(dicl)2]·MeOH·0.5H2O (2·MeOH·0.5H2O) were determined by X-ray crystallography. Magnetic studies show a large antiferromagnetic interaction, whereas a discrepancy appears between the low-temperature magnetic data and that predicted from an isotropic Hamiltonian model, indicating the influence of antisymmetric interactions. By using a different magnetic model with antisymmetric terms, the low-temperature susceptibility and magnetization data were fitted. The EPR data support the observation that 2 has isosceles or lower magnetic symmetry, whereas the antisymmetric exchange mechanism is used to identify the reported g values of the spectra. EPR studies also revealed that complex 2 keeps its structure in solution. The complexes interact with calf-thymus DNA by intercalation. The complexes, as well as [Cu2(dicl)4(H2O)2] (3), bind to albumins with relatively high binding constants. The highest cytotoxicity of the diclofenac compounds was observed after 24 h of incubation, whereas HL-60 cells recovered after 72 h of incubation in the presence of each compound. Moreover, complex 3 was the most cytotoxic among the compounds, and complex 2 was as cytotoxic as Nadicl.
Databáze: OpenAIRE
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