Color tuning of a nickel complex with a novel N2S2 pyridine-containing macrocyclic ligand

Abel Tamayo, Jaume Casabó, Lluis Escriche, Carlos Lodeiro, Berta Covelo, Carlos D. Brondino, Raikko Kivekäs, Reijo Sillampää

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40 Citations (Scopus)


The novel pyridine-containing 14-membered macrocycle 3,11-dithia-7,17- diazabicyclo[11.3.1]heptadeca-1(17),13,-15-triene (L), which contains an N 2S2 donor set, was synthesized, and its protonation behavior was studied by absorption titration with CH3SO3H. The reaction of L with Pd(II) was studied spectroscopically, and the square-planar complex [Pd(L)](BF4) was isolated and characterized. The reactions between L and NiX2·6H2O (X = BF 4, ClO4) in ethanol or acetonitrile afforded the octahedral complexes [Ni(CH3CN)(H2O)(L)](X)2 and [Ni(H2O)2(L)](X)2, respectively. The square-planar complexes [Ni(L)](X)2 were obtained by heating these octahedral complexes. Spectrophotometric titrations of [Ni(L)](BF 4)2 were performed with neutral and negatively charged ligands. The color of nitromethane solutions of this square-planar complex turns from red to cyan, purple, blue, yellow-green, and pink following addition of halides, acetonitrile, water, pyridine, and 2,2′-bipyridine, respectively. X-ray structural analyses were carried out on the {[Ni(ClO4)(H 2O)(L)][Ni(H2O)2(L)]}(ClO4) 3, [Ni(CH3CN)(H2O)(L)](ClO4) 2, [{Ni(L)}2(μ-Cl)2](ClO4) 2, and [{Ni(L)}2(μ-Br)2]Br 2·2CH3NO2 complexes.

Original languageEnglish
Pages (from-to)1140-1149
Number of pages10
JournalInorganic Chemistry
Issue number3
Publication statusPublished - 6 Feb 2006


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