4.7 Article

The coordination chemistry of benzimidazole-5,6-dicarboxylic acid with Mn(II), Ni(II), and Ln(III) complexes (Ln = Tb, Ho, Er, Lu)

Journal

CRYSTAL GROWTH & DESIGN
Volume 8, Issue 7, Pages 2299-2306

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/cg7010106

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The first coordination chemistry of a multidentate ligand benzimidazole-5,6-dicarboxylic acid (H2L) was investigated, and six novel two-dimensional (2D) coordination polymers based on this ligand, namely, [MnL](n) (1), {[Ni2L2(H2O)(4)]center dot 3H(2)O}(n) (2), {[Tb(L)(HL)(H2O)]center dot H2O}(n) (3) and {[Ln(2)L(2)(HL)(2)(H2O)(2)]}(n) (Ln = Ho (4), Er (5), Lu (6)), were synthesized under hydrothermal conditions. Compund 1 shows a novel coordination network with 4(4)6(2) topology and contains unusual five-coordinated one-dimensional {Mn-O}(n) chains along the b-axis. Compound 2 is a 2D layer structure of 4.8(2) topology in the ab plane and displays a three-dimensional (3D) supramolecular network via multiple intermolecular hydrogen bonds. Compound 3 also shows a 4(4)6(2) topology, but its coordination network is completely different from compound 1. Compounds 4-6 were isostructural, and each Ln (Ln = Ho (4), Er (5), Lu (6)) center in the framework acts as a five-connected node to give rise to a unique network with a (3.4.6)(3(2).4.5.6(2).7(4)) topology in the ab plane. Six complexes exhibit six types of bridging modes of the ligand. The numbers of L ligands around the metal centers increase from 3 (Ni) to 4 (Mn) and finally to 5 (Ln) as a result of an increase in metal ionic radii. The temperature-dependent magnetic susceptibility data have been explained with the Fisher model, with parameters g = 2.05, J = -3.06 cm(-1) for 1, and g = 2.09, J = -0.35 cm(-1) for 2, indicating antiferromagnetic coupling. The luminescent properties of 3 were studied.

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