Dinuclear Ni(II)Mn(II) and Cu(II)Mn(II) complexes of the general formula [MMn(Lm,n)](ClO4)2 ((L2,3)2-, (L2,3)2-, (L2,4)2-, (L3,3)2-; M = Ni, Cu) are obtained as solvates, using the dinucleating macrocycles (Lm,n)2- (derived from the [2:1:1] condensation of 2,6-diformyl-4-methylphenol, NH2(CH2)mNH2 (m = 2-3) and NH2(CH2)nNH2 (n = 2-4). [NiMn(L2,3)](ClO4)2·2DMF crystallizes in the orthorhombic space group Pbca with a = 22.186(4), b = 22.855(3), c = 13.951(2) Å, V = 7074(2) Å3, and Z = 8. [NiMn(L2,4)](ClO4)2·2DMF crystallizes in the monoclinic space group P21/n with a = 15.330(4), b = 11.739(3), c = 20.829(5) Å, β = 101.05(2)°, V = 3678(1) Å3, and Z = 4. In both complexes the Ni(II) and Mn(II) ions are bridged by two endogenous phenolic oxygens of the macrocycle, with the Ni-Mn intermetallic separation of 3.145(2) Å for the former and 3.111(3) Å for the latter. In each complex the Ni(II) resides at the N2O2 site with the ethylene lateral chain and assumes a planar geometry. The Mn(II) at the N2O2 site with the trimethylene or tetramethylene lateral chain assumes a distorted six-coordinate geometry together with two DMF molecules. The M(II)Mn(II) (M = Ni, Cu) complexes are electrochemically converted to M(I)Mn(II) and M(II)Mn(III) complexes which are characterized by visible spectroscopy.
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