Wydział Chemii

Rafał Petrus

Adrian Kowaliński

Tadeusz Lis

Miłosz Siczek

Piotr Sobota

2025

Inorganic Chemistry

64

16020-16035

10.1021/acs.inorgchem.5c02206

Naukowa

Angielski

Artykuł

In this study, a series of rare-earth molecular cluster aggregates with the formula [M₉^RE(μ₄-OH)₂(μ₃-OH)₈(sal-R)₁₆]X (M^RE(III) = Y (1), Eu (2), Dy (3), Tm (4), Yb (5), Lu (6); X^– = Cl^– (1–2, 4–6), or DyCl₄^– (3); Hsal-R = alkyl salicylate with R = Me (2, 4–6), Et (3), or Me and Et (1)) were synthesized via the direct reaction of rare-earth chlorides (M^RECl₃) with in situ generated lithium or zinc methyl salicylate salts in a ROH/tetrahydrofuran (THF) solution (ROH = MeOH, EtOH) under controlled moisture conditions. Complexes 1–6 were investigated as surrogates for minor actinides, with the aim of immobilizing these species in alkaline-earth manganites. The manganites were obtained by thermal decomposition of mixtures comprising either [Ca(sal-Et)₂]_n (7) or [Ba(sal-Et)₂(THF)]_n (8) with [Mn₂(μ-OMe)₂(sal-Me)₄] (9) at 850 or 1100 °C. Thermolysis of compounds 7 and 9 in the presence of 0.22 or 1.11 mol % 1–6 at 1100 °C yielded M^RE-doped CaMnO₃ as the major phase, with variable amounts of CaMn₂O₄. Under analogous conditions, decomposition of 8 and 9 produced BaMnO₃:M^RE(III); transmission electron microscopy (TEM) also identified nanorod-like crystallites of M^REMnO₃. Alkaline-earth manganites, prepared via the aryloxide route, effectively incorporate M^RE(III) ions at the Ca(II)/Ba(II) sites.

Cluster chemistry, Ligands, Materials, Transition metals, Transmission electron microscopy

CC-BY

http://dx.doi.org/10.1021/acs.inorgchem.5c02206

https://www.acs.org/content/acs/en.html