Probing the 5f electrons in a plutonyl(vi) cluster complex

Abstract

We report the structural, spectroscopic and preliminary magnetic characterisation of a tri-metallic plutonyl(VI) polyoxometalate complex, K(11)[K(3)(PuO(2))(3)(GeW(9)O(34))(2)] x 12 H(2)O.

Electrospray ionization mass spectrometry of a cerium(III) phosphomolybdate complex: Condensed and gas-phase cluster chemistry

“…(4a)) and present as presumably an oxo-saturated ion in solution (see Section 3.6), is a new moiety to phosphomolybdate chemistry; isolation of Ce(III)PMo 10 [19,[21][22][23][24]. Condensed phase results do not support the first hypothetical structure for the cerium complexes as crystal structures suggest that the vacancy in the trivacant lacunary Keggin ion is too large to complex a Ln ion; however it does effectively coordinate the actinyl cation (AnO 2 2+ ) through equatorial binding sites due to the steric hindrance imposed by these species [25][26][27]. Also, only plenary Keggin ions have been shown to complex tetravalent transition metals, i.e., Zr and Hf [18] (h = 1-3; Fig.…”

Trends and new directions in the crystal chemistry of actinide oxo-clusters incorporated in polyoxometalates

“…61 Synthesis and luminescence properties of the closely related neptunyl(VI) and plutonyl(VI) containing system obtained from the [GeW 9 O 34 ] 10entity in water, were investigated later, with the generation of a similar single [Np VI O 2 ] 2+ or [Pu VI O 2 ] 2+ unit encapsulated between two trivacant polytungstate species. 62 In the case of the neptunyl(VI)-containing molecule, the authors were able to show the interest of the polyanionic moieties in preventing the water quenching over the {Np VI O 2 } 2+ luminescence. 63 In addition to this property, the ((Np VI or Pu VI )O 2 )[GeW 9 O 34 ] 16sandwich-like compounds are rapidly formed in solution in a near quantitative yield and were consequently considered for a potential utilization in actinyl cations separation.…”

Ultrafiltration separation of nanoscale Am(VI)-polyoxometalate clusters from lanthanides

“…Note that the An≡O axial bond distances in the POM are approximately 0.03 Å shorter than the bond distances in other oxoanion and organometallic compounds 16 . The different charge distributions in the interior and surface of POM tend to polarize the O≡An≡O axial bonds, thus leading to elongation of one bond and shortening of the other when the actinyl ion is vertically encapsulated within the vacancy site [17][18][19] . In sharp contrast, when Eu 3+ ions, a representative Ln(III) ion, react with the POM under the same conditions, only pure {Se6W46} crystals are isolated without the presence of any lanthanide ions in the structure.…”