Fullerene and endometallofullerene Kagome lattices with symmetry-forced spin frustration

Abstract

Salts of fullerene C₆₀˙⁻ and endometallofullerene Sc₃N@I_h-C₈₀˙⁻ radical anions with Bu₃MeP⁺ cations ((Bu₃MeP⁺)₃(C₆₀˙⁻)₃·C₆H₄Cl₂ (1) and (Bu₃MeP⁺)₃(Sc₃N@I_h-C₈₀˙⁻)₃·C₆H₄Cl₂ (2)) have been obtained. The C₃ symmetry of the Bu₃MeP⁺ cation provides 2D Kagome lattices with an equilateral triangle arrangement of fullerenes in accordance with trigonal crystal symmetry P31m. The C₆₀˙⁻ and Sc₃N@I_h-C₈₀˙⁻ radical anions preserve their monomeric forms in 1 and 2 with the S = 1/2 spin state down to 1.9 K. The close packing of the fullerene radical anions results in strong antiferromagnetic coupling of the spins with Weiss temperatures of −108 K for 1 and −43 K for 2. Compound 1 is a rare example of a magnetic system in which in spite of the strong magnetic coupling of spins no long-range ordering is observed down to 1.9 K. The ¹³C NMR spectra of the ¹³C enriched sample of 1 support the absence of the antiferromagnetic ordering of spins down to 1.5 K. Thus, the crystals of 1 preserve large spin frustration forced by the trigonal symmetry. Therefore, compound 1 is a promising candidate for the first observation of a quantum spin liquid (QSL) state in a fullerene-based system. Isostructural salt 2 is the first compound that contains monomeric paramagnetic Sc₃N@I_h-C₈₀˙⁻ radical anions stable down to 1.9 K, which show strong spin frustration. These data indicate the ability of endometallofullerenes to give exotic magnetic systems such as QSLs.