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Novel heterometallic tetranuclear Ln-Ti citrates, the precursors for the lanthanide titanates

The date of: 2025-08-28
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来源:X-MOL

The reaction of Ln chlorides with Na3[Ti(H2Citrate)2(HCitrate)]

·9H2O (H4Citrate is citric acid) in hot water brings about two similar series of complexes having a defect-dicubane structure, [Ln2Ti2O2(H2O)6(H2Citrate)2(HCitrate)2]·nH2O (Ln = La (1), Ce (2), Nd (3); n = 6, and Eu (4), Gd (5), Tb (6), Dy (7), Ho (8); n = 7). In each series, the complexes are isostructural with each other. For the heavier lanthanides, Er and Yb, formation of coordination polymers built of defect-dicubane fragments was found. Solid-state thermolysis of the complexes 1–8 was studied by means of TGA and DSC methods under argon and under air; it was shown that in the case of the air atmosphere the complexes 1 and 3–8 are the precursors for pure Ln2Ti2O7 oxide phases, which are valuable functional materials. As demonstrated by the electron microscopy study, the obtained titanates possess a nanoporous ceramic structure.




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