Hydroxido-supported and carboxylato bridge-driven aggregation for discrete [Ni4] and interconnected [Ni2]n complexes

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Chattopadhyay, Krishna ; Craig, Gavin A. ; Kundu, Animesh ; Bertolasi, Valerio ; Murrie, Mark ; Ray, Debashis (2016)

Four different carboxylato bridges have been efficiently utilized for growth of three tetranuclear nickel(II) complexes [Ni4(μ3-H2L)2(μ3-OH)2(μ1,3-CH3CO2)2](ClO4)2 (1), [Ni4(μ3-H2L)2(μ3-OH)2(μ1,3-C2H5CO2)2](ClO4)2·1/2H2O (2), and [Ni4(μ3-H2L)2(μ3-OH)2(μ1,3-O2C-C6H4-pNO2)2](ClO4)(p-NO2-C6H4-CO2)·DMF·5H2O (3) and one dinuclear nickel(II)-based chain complex {[Ni2(μ-H2L)(μ1,3-O2CCH2Ph)2(H2O)](ClO4)·1/2(CH3OH)}n (4). These were obtained via the reaction of Ni(ClO4)2·6H2O with H3L [2,6-bis((2-(2-hydroxyethylamino)ethylimino)methyl)-4-methylphenol] and RCO2Na (R = CH3,C2H5, p-NO2C6H4, and PhCH2). This family of complexes is developed from {Ni2(μ-H2L)}3+ fragments following self-aggregation. The complexes were characterized by X-ray crystallography and magnetic measurements. The changes from acetate, propionate, and p-nitrobenzoate to phenylacetate groups resulted in two different types of coordination aggregation. These compounds are new examples of [Ni4] and [Ni2]n complexes where organization of the building motifs are guided by the type of the carboxylate groups responsible for in-situ generation and utilization of HO– bridges with alteration in the aggregation process within the same ligand environment. Studies on the magnetic behavior of the compounds reveal that the exchange coupling within 1–4 is predominantly antiferromagnetic in nature.
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