Abstract
Tris(β-diketonato)ruthenium(III) complexes of mononuclear [Ru(acac)3] and binuclear [{Ru(acac)2}2(μ-OEt)2] are spin-1/2 quantum spin magnets. In both system, Ru and surrounding O6 atoms consist of octahedral geometry, and in the binuclear complex, two (acetylacetonato) ruthenium complexes are bridged by two oxygen atoms of ethoxyl groups, making up a dimer with Ru-Ru bond. The electronic state of ruthenium is easily controlled by changing the methyl groups on the acetylacetone to the different substituents such as electronegative trifluoromethyl group. We expect to introduce a new degree of freedom, a charge fluctuation into the dimer spin system. In this study, we investigate the spin state of monomer and dimer quantum spin systems by means of 13C, 19F, 101Ru-NMR at low temperatures. In the former [Ru(acac)3], we observed Curie-like temperature dependence in the Knight shift down to 1.5 K, indicating that the system was simply in the paramagnetic state. The dimer system [{Ru(acac)2}2(μ-OEt)2] on the other hand showed the NMR signal with very long T1 at zero shift position at low temperatures, indicating that the system was the spin singlet state. In order to investigate the effect of substitution, we also report on results of mer-[Ru(ehfa)3] and [Ru(fhea)3], for which methyl groups are substituted by trifluoromethyl groups.
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