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An unexpected polyhydroxyl-bridged tetranuclear ZnII complex and a benzoquinone compound derived from metal-ion promoted reactivity of Schiff base ligands were synthesized and characterized. The reaction of zinc(II) acetate dihydrate with oxime-type Schiff base ligand HL1 [HL1 = 1-(3-((3,5-dibromosalicylaldehyde)amino)phenyl) ethan-1-one O-benzyl oxime] in methanol, acetone and acetonitrile resulted in the chemoselective cleavage of the C=N bond of the Schiff base HL1 and then the further addition of acetone to two salicylaldehyde molecules derived from cleavage of the C=N bond in situ α,α double aldol reaction promoted by ZnII ions. The newly formed ligands H4L2 coordinate to four ZnII ions forming a defect-dicubane core structure [ZnII 4(H2L2)2(μ3-OCH3)2(μ-OCH3)2(CH3OH)2] (1) bridged exclusively by oxygen-based ligands. The similar ligand HL3 [HL3 = 1-(3- ((3,5-dichlorosalicylaldehyde)amino)phenyl)ethan-1-one O-benzyl oxime)] was employed to react with CdII acetate dihydrate under the same reaction conditions. No aldol addition occurred but a unexpected benzoquinone compound 2,5-bis(((3-(1-((benzyloxy)imino)ethyl) phenyl)imino)methyl)-1,4-benzoquinone (2) formed. The results provided interesting insights into one-pot routes involving in situ reactions act as a strategy for obtaining a variety of polymeric/polynuclear complexes which are inconvenient to obtain from directly presynthesizing the ligands. [ABSTRACT FROM AUTHOR]

Based on the bis-triazole ligand 2, 6-bis(1, 2,4-triazole-4-yl)pyridine (L), the triazole-iron(II) complexes [Fe(L)2(dca)2(H2O)2] ·2H2O ( 1) (Nadca = sodium dicyanamide), {[Fe(μ2-L)2(H2O)2]Cl2} n ( 2), and {[Fe(μ2-L)2(H2O)2](ClO4)2 ·L ·H2O} n ( 3) were isolated by solvent diffusion methods. When iron(II) salts and Nadca were used, compound 1 was isolated, which contains mononuclear Fe(L)2(dca)2(H2O)2 units. When FeCl2 or FeClO4 were used, one-dimensional (1D) cation iron(II) chains ( 2) and two-dimensional (2D) cation iron(II) networks ( 3) were isolated indicating anion directing structural diversity. Moreover, variable-temperature magnetic susceptibility data of 1- 3 were recorded in the temperature range 2-300 K. The magnetic curve of complex 2 was fitted by using the classical spin Heisenberg chain model indicating anti-ferromagnetic interactions ( J = -5.31 cm-1). Obviously complexes 1- 3 show no detectable thermal spin crossover behaviors, the lack of spin-crossover behavior may be correlated with FeN4O2 coordination spheres in 1- 3. [ABSTRACT FROM AUTHOR]