Harnessing electron transfer from the perchlorotriphenylmethide anion to Y@C82(C(2v)) to engineer an endometallofullerene-based salt.

We show that electron transfer from the perchlorotriphenylmethide anion (PTM(-)) to Y@C82(C2v) is an instantaneous process, suggesting potential applications for using PTM(-) to perform redox titrations of numerous endohedral metallofullerenes. The first representative of a Y@C82-based salt containing the complex cation was prepared by treating Y@C82(C2v) with the [K(+)([18]crown-6)]PTM(-) salt. The synthesis developed involves the use of the [K(+)([18]crown-6)]PTM(-) salt as a provider of both a complex cation and an electron-donating anion that is able to reduce Y@C82 C2v). For the first time, the molar absorption coefficients for neutral and anionic forms of the pure isomer of Y@C82(C2v) were determined in organic solvents with significantly different polarities.

EPR spectrum of the Y@C82 metallofullerene isolated in solid argon matrix: hyperfine structure from EPR spectroscopy and relativistic DFT calculations.

The EPR spectrum of the Y@C(82) molecules isolated in solid argon matrix was recorded for the first time at a temperature of 5 K. The isotropic hyperfine coupling constant (hfcc) A(iso) = 0.12 +/- 0.02 mT on the nucleus (89)Y as derived from the EPR spectrum is found in more than two times greater than that obtained in previous EPR measurements in liquid solutions. Comparison of the measured hfcc on a metal atom with that predicted by density-functional theory calculations (PBE/L22) indicate that relativistic method provides good agreement between experiment in solid argon and theory. Analysis of the DFT calculated dipole-dipole hf-interaction tensor and electron spin distribution in the endometallofullerenes with encaged group 3 metal atoms Sc, Y and La has been performed. It shows that spin density on the scandium atom represents the Sc d(yz) orbital lying in the symmetry plane of the C(2v) fullerene isomer and interacting with two carbon atoms located in the para-position on the fullerene hexagon. In contrast, the configuration of electron spin density on the heavier atoms, Y and La, is associated with the hybridized orbital formed by interaction of the metal d(yz) and p(y) electronic orbitals.