Modulation of Nuclearity in Cu^II−Mn^II Complexes of a N₂O₂ Donor Ligand Depending upon Carboxylate Anions: Structures, Magnetic Properties and Catalytic Oxidase Activities

Abstract

Three new hetero-metallic copper(II)-manganese(II) complexes, [(CuL)₂ Mn₃ (C₆ H₅ CO₂ )₆ ] (1), [(CuL)₂ Mn(CH₃ CO₂ )₂ ] (2), and {[(CuL)₂ Mn(C₆ H₅ CH₂ CO₂ )₂ ] ⋅ 2CH₃ CN} (3), have been synthesized using [CuL] as ''metalloligand'' (where H₂ L=N,N'-bis(2-hydroxynaphthyl-methylidene)-1,3-propanediamine). Single-crystal structural analyses show an almost linear penta-nuclear structure for complex 1 where a square planar [CuL] unit is connected to each of the two terminal Mn^II ions of a linear, centrosymmetric [Mn₃ (benzoate)₆ ] unit through the double phenoxido bridges. Both complexes 2 and 3 possess a linear tri-nuclear structure where two terminal square-pyramidal [CuL] units are bonded to the central Mn^II ion through double phenoxido oxygen atoms along with a syn-syn bridging acetate (for 2)/phenyl acetate (for 3). All three complexes exhibit catecholase, and phenoxazinone synthase-like activities under aerial conditions. For catecholase like activity, the turnover numbers (k_cat ) are 595, 40, and 205 h^-1 whereas, for phenoxazinone synthase like activity, the turnover numbers are 25, 4, and 11 h^-1 for complexes 1-3, respectively. The mechanism of both catalytic oxidase activities is proposed on the basis of mass spectral evidences. Variable-temperature (2-300 K) dc molar magnetic susceptibility measurements of 1 reveal antiferromagnetic interactions between the Cu-Mn centres (J₁ =-29.3 cm^-1 ), and also between the Mn-Mn centres of the [Mn₃ (benzoate)₆ ] unit (J₂ =-0.68 cm^-1 ). On increasing the magnetic field at 2 K, its ground spin state changes from S=3/2 to S=5/2 at 4 T, attributable to the low value of J₂ which makes the excited spin states close in energy with the ground spin state. Complexes 2 and 3 show antiferromagnetic coupling interactions between the Cu-Mn pairs with J values of -9.51, and -5.32 cm^-1 , respectively.