Effective magnetic coupling with strong spin frustration in (Ph3MeP+)(C60•-) and reversible C60•- dimerization in (Ph3MeP+)(C60•-)·C6H5CN. Effect of solvent on structure and properties

Abstract

Solvent free and solvent containing salts of the C60•- radical anions with the triphenylmethylphosphonium cations, (Ph3MeP+)(C60•-) (1) and (Ph3MeP+)(C60•-)·C6H5CN (2), have been obtained. The salts show different structures and physical properties. Complex 1 has double chains from C60•- with triangular fullerene arrangement and short interfullerene center-to-center distances of 10.079(1)-10.103(1) Å. No dimerization is observed in 1 preserving unpaired spins down to 1.9 K and providing magnetic moment of 1.68 μB at 300 K. Weiss temperature of Θ = -60 K indicates a strong antiferromagnetic coupling of spins. In spite of that, no magnetic ordering is observed down to 1.9 K showing that 1 has strong frustration of spins (f = Θ/TN > 30) due to triangular fullerene lattice. Compound 2 additionally contains the C6H5CN solvent molecules and has a layered structure with fullerene hexagons accommodating the Ph3MeP+ cations and C6H5CN solvent molecules in the center. Interfullerene center-to-center distances vary in the fullerene layers in the 9.921(2)-10.066(2) Å range. Fullerenes dimerize reversibly in pairs with a shortest interfullerene center-to-center distance of 9.921(2) Å below 220 K to form diamagnetic singly-bonded (C60-)2 dimers.