Tetranuclear lanthanide(III) complexes in a seesaw geometry: synthesis, structure, and magnetism

Joydeb Goura; James P S Walsh; Floriana Tuna; Vadapalli Chandrasekhar

doi:10.1021/ic4027915

Tetranuclear lanthanide(III) complexes in a seesaw geometry: synthesis, structure, and magnetism

Inorg Chem. 2014 Apr 7;53(7):3385-91. doi: 10.1021/ic4027915. Epub 2014 Mar 10.

Authors

Joydeb Goura¹, James P S Walsh, Floriana Tuna, Vadapalli Chandrasekhar

Affiliation

¹ Department of Chemistry, Indian Institute of Technology Kanpur , Kanpur-208016, India.

PMID: 24611541
DOI: 10.1021/ic4027915

Abstract

The reaction of 2-methoxy-6-(pyridin-2-ylhydrazonomethyl)phenol (LH) with Ln(III) (Ln = Gd, Tb, Dy, Ho) salts in the presence of an excess of triethylamine afforded [Gd4(L)4(μ4-OH)(μ3-OH)2(NO3)4]·(NO3)·4CH3CN·CH3OH·2H2O (1), [Tb4(L)4(μ4-OH)(μ3-OH)2(NO3)4]·(NO3)·4CH3CN·3H2O (2), [Dy4(L)4(μ4-OH)(μ3-OH)2(NO3)4]·(NO3)·6CH3CN·H2O (3), and [Ho4(L)4(μ4-OH)(μ-OH)2(NO3)4]·(NO3)·8CH3CN·3CH3OH·2H2O (4). All four complexes contain a monocationic tetranuclear core with a unique seesaw topology. The tetranuclear assembly is formed through the coordination of four [L](-), one μ4-OH, two μ3-OH, and four chelating nitrate ligands, with a charge-balancing nitrate counteranion. Magnetic studies reveal a weak antiferromagnetic coupling throughout the series. Compound 1 can be modeled well with an isotropic exchange between all centers parametrized by J = -0.09 cm(-1). Compound 3 exhibits slow magnetic relaxation at low temperatures.