Heterometallic 3d–4f Alkoxide Precursors for the Synthesis of Binary Oxide Nanomaterials

[Image: see text] In this study, a new method for the synthesis of heterometallic 3d–4f alkoxides by the direct reaction of metallic lanthanides (La, Pr, Nd, Gd) with MCl(2) (M = Mn, Ni, Co) in 2-methoxyethanol was developed. The method was applied to the synthesis of the heterometallic oxo-alkoxide clusters [Ln(4)Mn(2)(μ(6)-O)(μ(3)-OR)(8)(HOR)(x)Cl(6)] (Ln = La (1), Nd (2), Gd (3); x = 0, 2, 4); [Pr(4)M(2)(μ(6)-O)(μ(3)-OR)(8)(HOR)(x)Cl(6)] (M = Co (4), Ni (5); x = 2, 4); and [Ln(4)Mn(2)(μ(3)-OH)(2)(μ(3)-OR)(4)(μ-OR)(4)(μ-Cl)(2)(HOR)(4)Cl(6)] (Ln = La (11) and Pr (12)). Mechanistic investigation led to the isolation of the homo- and heterometallic intermediates [Pr(μ-OR)(μ-Cl)(HOR)Cl](n) (6), [Co(4)(μ(3)-OR)(4)(HOR)(4)Cl(4)] (7), [Ni(4)(μ(3)-OR)(4)(HOEt)(4)Cl(4)] (8), [Mn(4)(μ(3)-OR)(4)(HOR)(2)(HOEt)(2)Cl(4)] (9), and [Nd(HOR)(4)Cl][CoCl(4)] (10). In the presence of an external M(II) source at 1100 °C, 1–4 and 12 were selectively converted into binary metal oxide nanomaterials with trigonal or orthorhombic perovskite structures, i.e., LaMnO(3), GdMnO(3), NdMnO(3), Pr(0.9)MnO(3), and PrCoO(3). Compound 5 decomposed into a mixture of homo- and heterometallic oxides. The method presented provides a valuable platform for the preparation of advanced heterometallic oxide materials with promising magnetic, luminescence, and/or catalytic applications.