Hydroxido-Supported and Carboxylato Bridge-Driven Aggregation for Discrete [Ni4] and Interconnected [Ni2]nComplexes.
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]ncomplexes 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.
Department of Chemistry, Indian Institute of Technology , Kharagpur 721 302, India.
Krishna
K
Chattopadhyay
School of Chemistry, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
Gavin A
GA
Craig
Department of Chemistry, Indian Institute of Technology , Kharagpur 721 302, India.
Animesh
A
Kundu
Dipartimento di Scienze Chimiche e Farmaceutiche, Centro di Strutturistica Diffrattometrica, University of Ferrara , 44121 Ferrara, Italy.
Valerio
V
Bertolasi
School of Chemistry, University of Glasgow , Glasgow G12 8QQ, United Kingdom.
Mark
M
Murrie
Department of Chemistry, Indian Institute of Technology , Kharagpur 721 302, India.
Debashis
D
Ray