Rational design of large-spin clusters based on the hexacopper(II) siloxanolate coreстатья
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Дата последнего поиска статьи во внешних источниках: 18 марта 2017 г.
Аннотация:The hexacopper(II) siloxanolate cage [Cu6{(PhSiO2)6}2(BuOH)5]·3 nBuOH has been synthesized by reaction between CuCl2 and potassium phenylsiloxanolate in n-butanol, and characterized by single-crystal X-ray diffraction, magnetic measurements and high-frequency EPR (HF-EPR). The complex exhibits a torus-like structure featuring a layer of six copper(II) ions sandwiched between two cyclic (PhSiO2)66– ligands and surrounded by nBuOH molecules. The magnetic properties are characterized by moderate ferromagnetic exchange interactions between the S = 1/2 copper(II) centres to give an S = 3 ground spin state. Variable temperature HF–EPR spectra evidence a hard-axis magnetic anisotropy with g|| = 2.063, g⊥ = 2.225 and D = 0.31 cm–1. The cage is very soluble in organic solvents and, upon exchange of the labile nBuOH ligands, it functions as a high-spin hexatopic receptor for monodentate units. Reaction with the trigonal bipyramidal copper(II) mononuclear [Cu(tmpa)CN]+ in CHCl3/MeOH solution (tmpa = tris(2-pyridylmethyl)amine) affords the decacopper(II) complex [Cu6{(PhSiO2)6}2{NCCu(tmpa)}4](PF6)4, whose X-ray structure and magnetic behaviour are presented.