[An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory

We have reported a general and straightforward synthesis scheme for high-yield preparation of single-crystals of the oxidation-sensitive compounds 1(U-Pu), while a micro-synthesis approach was used for 1(Cf) owing to the scarcity and hard gamma emission of 249Cf. These compounds, in particular 1(U), may serve as alternative precursors to the well-established UI3(thf)4 and the recently introduced UI3 and U(CF3SO3)3.[ , ,12] In addition, we find that for similar An3+/Ln3+ ionic radii the [An(H2O)9]3+ and [Ln(H2O)9]3+ cation structures in 1(M) are almost identical. This reflects the electrostatic nature of the An/Ln-O bonds and thus suggests that the local structure of the hydrated ions in solution may also be similar. Finally, the magnetic susceptibilities of 1(U-Am) may be fully reproduced by ligand-field calculations, from which we can derive the 5f electronic level structures.

APOSTOLIDIS Christos;  SCHIMMELPFENNIG Bernd;  MAGNANI Nicola;  LINDQVIST-REIS Patric;  WALTER Olaf;  SYKORA Richard;  MORGENSTERN Alfred;  COLINEAU Eric;  CACIUFFO Roberto;  KLENZE R.;  HAIRE Richard;  REBIZANT J.;  BRUCHERTSEIFER Frank;  FANGHAENEL Thomas; 

2010-08-04

WILEY-V C H VERLAG GMBH

JRC57372

1433-7851,   

https://publications.jrc.ec.europa.eu/repository/handle/JRC57372,   

10.1002/anie.201001077,