6533b873fe1ef96bd12d5f4e

RESEARCH PRODUCT

Homo- and Heterobinuclear Cu2+ and Zn2+ Complexes of Ditopic Aza Scorpiand Ligands as Superoxide Dismutase Mimics

Lluis GuijarroSandra TreflerAntonio Garcia-españaJavier Pitarch-jarqueEnrique García-españaMario InclánBegoña VerdejoJavier U. ChicoteAntonio Doménech-carbó

subject

biology010405 organic chemistryChemistryLigandStereochemistryMetal ions in aqueous solutionCrystal structure010402 general chemistry01 natural sciences0104 chemical sciencesInorganic ChemistrySuperoxide dismutaseCrystallographybiology.proteinPhysical and Theoretical ChemistryCyclic voltammetrySpectroscopyStoichiometry

description

Two polytopic aza-scorpiand-like ligands, 6-[7-(diaminoethyl)-3,7-diazaheptyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L1) and 6-[6′-[3,6,9-triaza-1-(2,6-pyridina)cyclodecaphan-6-yl]-3-azahexyl]-3,6,9-triaza-1-(2,6-pyridina)cyclodecaphane (L2), have been synthesized. The acid–base behavior and Cu2+, Zn2+, and Cu2+/Zn2+ mixed coordination have been analyzed by potentiometry, cyclic voltammetry, and UV–vis spectroscopy. The resolution of the crystal structures of [Cu2L2Cl2](ClO4)2·1.67H2O (1), [Cu2HL2Br2](ClO4)3·1.5H2O (2), and [CuZnL2Cl2](ClO4)2·1.64H2O (3) shows, in agreement with the solution data, the formation of homobinuclear Cu2+/Cu2+ and heterobinuclear Cu2+/Zn2+ complexes. The metal ions are coordinated within the two macrocyclic cavities of the ligand with the involvement of a secondary amino group of the bridge in the case of 1 and 3. Energy-dispersive X-ray spectroscopy confirms the 1:1 Cu2+/Zn2+ stoichiometry of 3. The superoxide dismutase (SOD) activities of the Cu2+/Cu2+ and Cu2+/Zn2+ co...

https://doi.org/10.1021/acs.inorgchem.7b01756