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

Six new solvent-free, homoleptic paramagnetic tris(alkyl)lanthanides Ln{C(SiHMe 2 ) 3 } 3 ( 1Ln ) and Ln{C(SiHMe 2 ) 2 Ph} 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 LnC 3 core, and six secondary interactions involving Ln↼H-Si bonding in Ln{C(SiHMe 2 ) 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(SiHMe 2 ) 3 } 3 ( 1La , Z = 2, Z ' = 1) and La{C(SiHMe 2 ) 2 Ph} 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 χ m 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 μ B ) and 1Dy ( M ≈ 6 μ B ) matches the experimental values, while the computed value for 2Dy better matches the value measured for 2Dy diluted in 2La ( M ≈ 5 μ B ). 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 .