Abstract
The interaction between the radical anions C60 ·− and divalent d- and f-metal (Co, Fe, Ni, Mn, Eu, Cd) cations in DMF and acetonitrile-benzonitrile (AN-BN) mixture was studied. Black solid polycrystalline salts (C60 ·−)2{(M2+)(DMF) x } (x = 2.4–4, 1–6) containing the radical anions C60 ·− and metal(ii) cations solvated by DMF were prepared for the first time and their optical and magnetic properties were studied. The salts containing Co2+, Fe2+, and Ni2+ are characterized by antiferromagnetic interactions between the radical anions C60 ·−, which result in unusually large broadening of the EPR signal of C60 ·− upon lowering the temperature (from 5.55–12.6 mT at room temperature to 35–40 mT at 6 K for Co2+ and Ni2+). The salts containing Mn2+ and Eu2+ form diamagnetic dimers (C60 −)2, which causes a jumpwise decrease in the magnetic moment of the complexes and disappearance of the EPR signal of C60 ·− in the temperature range 210–130 K. A feature of salt 6 is magnetic isolation of the radical anions C60 ·− due to the presence of diamagnetic cation Cd2+. The salts prepared are unstable in air and decompose in o-dichlorobenzene or AN. Reactions of C60 ·− with metal(ii) cations in AN-BN mixture result in decomposition products of the salts that contain neutral fullerene dimers and metals solvated by BN.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1909–1919, September, 2008.
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Konarev, D.V., Lyubovskaya, R.N. Magnetic properties of fullerene salts containing d- and f-metal cations (Co2+, Ni2+, Fe2+, Mn2+, Eu2+, Cd2+). Specific features of the interaction between C60 ·− and the metal cations. Russ Chem Bull 57, 1944–1954 (2008). https://doi.org/10.1007/s11172-008-0261-y
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DOI: https://doi.org/10.1007/s11172-008-0261-y