Complexes of click-derived bistriazolylpyridines: remarkable electronic influence of remote substituents on thermodynamic stability as well as electronic and magnetic properties

Chemistry : a European Journal
Marc OstermeierStefan Hecht

Abstract

2,6-Bis(1,2,3-triazol-4-yl)pyridine (btp) ligands with substitution patterns ranging from strongly electron-donating to strongly electron-accepting groups, readily prepared by means of Cu-catalyzed 1,3-dipolar cycloaddition (the "click" reaction), were investigated with regard to their complexation behavior, and the properties of the resulting transition-metal compounds were compared. Metal-btp complexes of 1:1 stoichiometry, that is, [Ru(btp)Cl(2)(dmso)] and [Zn(btp)Br(2)], could be isolated and were crystallographically characterized: they display octahedral and trigonal-bipyramidal coordination geometries, respectively, and exhibit high aggregation tendencies due to efficient pi-pi stacking leading to low solubilities. Metal-btp complexes of 1:2 stoichiometry, that is, [Fe(btp)(2)](2+) and [Ru(btp)(2)](2+), could also be synthesized and their metal centers show the expected octahedral coordination spheres. The iron compounds exhibit quite a complex magnetic behavior in the solid state including spin crossover near room temperature, and hysteresis and locking into high-spin states on tempering at 400 K, depending on the substituents on the btp ligands. Cyclic voltammetry studies of [Ru(btp)(2)](2+) reveal strong modulation of...Continue Reading

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Citations

Jan 4, 2012·Journal of Molecular Recognition : JMR·Rajesh GhaiBrett M Collins
Dec 22, 2017·Chemistry : a European Journal·Iweta Pryjomska-RayChristian Limberg
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