Abstract
A phenol-based dinucleating macrocycle, L 2−, comprising two 2-( N-methyl)aminomethyl-6-iminomethyl-4-bromophenolate moieties combined by a -(CH 2) 2- chain at the amino nitrogens and by a -(CH 2) 3- chain at the imino nitrogens and having dissimilar N(amine) 2O 2 and N(imine) 2O 2 metal-binding sites sharing the phenolic oxygens, is obtained as the mononuclear Cu II complex [Cu(L)]. The 2-propanol adduct, [Cu(L)]·2-PrOH, crystallizes in a triclinic crystal system, space group P1 (No. 2) with Z = 2, a = 11.621(6), b = 14.17(1), c = 9.390(4) Å, α = 96.59(6), β = 107.78(3), γ = 103.78(5)°, V = 1400(1) Å 3. The crystallography reveals that the Cu II resides in the N(imine) 2O 2 site and has a nearly planar geometry. A series of dinuclear Cu IIM II complexes CuM(L)Cl 2 (M = Mn, Co, Ni, Cu, Zn) are obtained by reacting [Cu(L)] with metal(II) chloride salts. The methanol adduct of the CuNi complex, [CuNi(L)Cl 2]·MeOH, crystallizes in a monoclinic crystal system, space group P2 1/ a (No. 14) with Z = 4, a = 14.495(4), b = 13.034(4), c = 14.978(3) Å, β = 91.89(2)°, V = 2828(1) Å 3. The methanol adduct of the CuZn complex, [CuZn(L)Cl 2]·MeOH, crystallizes in a monoclinic crystal system, space group P2 1/ a (No. 14) with Z = 4, a = 14.680(4), b = 12.942(3), c = 15.149(4) Å, β = 91.25(2)°, V = 2877(1) Å 3. The X-ray crystallography for the two complexes reveal that the Cu II ion resides in the N(imine) 2O 2 site with the M II (Ni II or Zn II) ion in the N(amine) 2O 2 site. In each complex the Cu II and M II ions have nearly square-pyramidal geometry with the chloride ion occupying apical positions. Cryomagnetic studies (4.2–300 K) indicate a significant antiferromagnetic interaction within each dinuclear unit except for the case of the CuZn complex.
Published Version
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