The Reversible Formation of a Single-Bonded (C<sub>60</sub><sup>-</sup>)<sub>2</sub> Dimer in Ionic Charge\nTransfer Complex: Cp*<sub>2</sub>Cr·C<sub>60</sub>(C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub>. The Molecular Structure of (C<sub>60</sub><sup>-</sup>)<sub>2</sub>
Dmitri V. Konarev (1405348)Salavat S. Khasanov (1405330)Akihiro Otsuka (1405342)Gunzi Saito (1405345)
Abstract
A new ionic complex of C<sub>60</sub> with decamethylchromocene, Cp*<sub>2</sub>Cr·C<sub>60</sub>(C<sub>6</sub>H<sub>4</sub>Cl<sub>2</sub>)<sub>2</sub> (<b>1</b>), has been obtained. The fullerides are monomeric in <b>1</b> at room temperature, whereas they form a single-bonded (C<sub>60</sub><sup>-</sup>)<sub>2</sub> dimer at low temperatures, the structure of which has been studied by the X-ray diffraction on a single crystal at 100 K. The length of the intercage C−C bond is 1.597(7) Å and the interfullerene distance is equal to 9.28 Å. A phase transition attributed to the reversible C<sub>60</sub><sup>•-</sup> dimerization is observed in the 220−200 K range. The transition is accompanied by changes in the unit cell parameters, the decrease of the magnetic moment from 4.20 μ<sub>B</sub> (<i>S</i> = <sup>3</sup>/<sub>2</sub>, <sup>1</sup>/<sub>2</sub>) to 3.88 μ<sub>B</sub> (<i>S</i> = <sup>3</sup>/<sub>2</sub>) and the appearance of EPR signal from Cp*<sub>2</sub>Cr<sup>+</sup>, simultaneously.
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