Heterometallic {Fe18M6} (M = Y, Gd, Dy) Pivalate Wheels Display Solvent-Induced Polymorphism

A new series of heterometallic wheels, isolated as [Fe18M6(piv)12(Htea)18(tea)6(N3)6]·n(solvent) (MIII = Y (1a, 1b), Gd (2a, 2b), and Dy (3a, 3b); Hpiv = pivalic acid, H3tea = triethanolamine), forms by the reaction of trinuclear μ3-oxo-linked or hexanuclear μ-OH-linked Fe(III) pivalate clusters with rare earth nitrates, H3tea, and azide ligands in MeOH/MeCN or EtOH/MeCN media under ultrasonic irradiation. Single-crystal X-ray diffraction showed that wheels 1a–3a prepared from MeOH/MeCN solutions crystallize in the triclinic space group P1̅ and have Ci symmetry, whereas wheels 1b–3b received from EtOH/MeCN solution crystallize in the trigonal space group R3̅ and have C3i symmetry. Magnetic studies reveal medium antiferromagnetic exchange interactions within the Fe3 trimeric unit (with the exchange coupling parameters of JFe3 = −13.1 cm–1 for 1a, JFe3 = −11.6 cm–1 for 1b) and weak intermolecular antiferromagnetic exchange interactions (λmf = −0.366 mol cm–3 and −0.368 mol cm–3 (zJmf = −0.19 cm–1), respectively). This leads to spin ground states of S = 5/2 for each {Fe3} unit. Substitution of diamagnetic Y(III) centers by paramagnetic Ln(III) centers (in 2a/2b by Gd(III) and in 3a/3b by Dy(III) centers) results in ferromagnetic exchange interactions between the Fe(III) and Ln(III) centers in addition to the predominant antiferromagnetic Fe···Fe interactions in 1a/1b.