Structure and Magnetic Properties of Homoleptic Trivalent Tris(alkyl)lanthanides

Abstract

Six new solvent-free, homoleptic paramagnetic tris­(alkyl)­lanthanides Ln­{C­(SiHMe2)3}3 (1Ln) and Ln­{C­(SiHMe2)2Ph}3 (2Ln) (Ln = Gd, Dy, and Er) were synthesized to investigate the magnetic properties of 4f organometallic compounds stabilized by secondary Ln↼H–Si and benzylic interactions. The unit cell of 1Gd contains one independent molecule (Z = 2), while 1Dy and 1Er crystallize with four independent isostructural molecules per unit cell (Z = 16). In all molecules, as in other 1Ln compounds, the three tris­(dimethylsilyl)­methyl ligands form a trigonal planar LnC3 core, and six secondary interactions involving Ln↼H–Si bonding in Ln­{C­(SiHMe2)3}3 form above and below the equatorial plane. Two and five crystallographically independent molecules of each 2Ln (2Gd, Z = 8; 2Dy, Z = 20) form with three π-coordinated phenyl groups in addition to either one or two secondary Ln↼H–Si interactions per molecule. The packing of these midseries organolanthanide compounds contrasts the single crystallographically unique molecules in previously reported La­{C­(SiHMe2)3}3 (1La, Z = 2, Z′ = 1) and La­{C­(SiHMe2)2Ph}3 (2La, Z = 2, Z′ = 1/3). 2La doped with 2Dy can adopt the crystallographic structure of 2La, which promotes magnetic properties, namely a higher χm T value at low temperatures as well as stronger magnetic anisotropy. The ac susceptibility data for 10% 2Dy doped into 2La suggests slow relaxation at low temperatures with a relaxation barrier of ∼45 K. The computed saturated magnetization of 1Er (M ≈ 4.5 μB) and 1Dy (M ≈ 6 μB) matches the experimental values, while the computed value for 2Dy better matches the value measured for 2Dy diluted in 2La (M ≈ 5 μB). Gas-phase calculations predict that the ground-state and first excited-state multiplet separations are larger for 1Er than 2Er, while the ordering for dysprosium is 1Dy > 2Dy.