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The stability of the novel Pu(IV) silicate, Cs2PuSi6O15, was predicted from a combination of crystal chemical reasoning and DFT calculations and confirmed by its synthesis via flux crystal growth. Formation...

Na n MAn 6 F 30 is an extremelyv ersatile framework structure for incorporating tetravalent actinides (An) and cerium along with divalent or trivalent d-metals (M); moreover,t he structuree xhibits ah igh resistancet oh arsh chemical conditions. This extreme robustnessc an potentially be exploited fort he sequestration of plutonium in a stable matrix;h owever, no Na n MPu 6 F 30 compounds have been reported so far.Herein, we present four new plutonium fluorides that have been prepared as single crystals by mild hydrothermals ynthesis methods. Structural characterizations revealed their compositionst ob eNa 3 AlPu 6 F 30 , Na 3 FePu 6 F 30 ,N a 3 CoPu 6 F 30 ,a nd Na 2.4 Mn 1.6 Pu 6 F 30 .S urprisingly,i nt he plutonium series, it was found that Co 2 + and Mn 2 + precursors oxidized to form Na 3 Co III Pu 6 F 30 and Na 2.4 Mn II/III 1.6 Pu 6 F 30 ,w hereas the analogous reactionsf or cerium result in reduction of the transition metal, even when beginning with aM 3 + precursor.W hile cerium is often used as as urrogate for plutonium, this work serves as an example that deviationsb etween their chemistries do occur.