Molecular solids of actinide hexacyanoferrate: Structure and bonding
Den Auwer, C.
Galbis Fuster, Elsa
Rodríguez Pappalardo, Rafael
Sánchez Marcos, Enrique
|Department||Universidad de Sevilla. Departamento de Química Física|
|Abstract||The hexacyanometallate family is well known in transition metal chemistry because the remarkable electronic delocalization along the metal-cyano-metal bond can be tuned in order to design systems that undergo a reversible ...
The hexacyanometallate family is well known in transition metal chemistry because the remarkable electronic delocalization along the metal-cyano-metal bond can be tuned in order to design systems that undergo a reversible and controlled change of their physical properties. We have been working for few years on the description of the molecular and electronic structure of materials formed with [Fe(CN)6]n- building blocks and actinide ions (An = Th, U, Np, Pu, Am) and have compared these new materials to those obtained with lanthanide cations at oxidation state +III. In order to evaluate the influence of the actinide coordination polyhedron on the three- dimensional molecular structure, both atomic number and formal oxidation state have been varied : oxidation states +III, +IV. EXAFS at both iron K edge and actinide LIII edge is the dedicated structural probe to obtain structural information on these systems. Data at both edges have been combined to obtain a three-dimensional model. In addition, qualitative electronic information has been gathered with two spectroscopic tools : UV-Near IR spectrophotometry and low energy XANES data that can probe each atom of the structural unit : Fe, C, N and An. Coupling these spectroscopic tools to theoretical calculations will lead in the future to a better description of bonding in these molecular solids. Of primary interest is the actinide cation ability to form ionic – covalent bonding as 5f orbitals are being filled by modification of oxidation state and/or atomic number.
|Citation||Dupouy, G., Dumas, T., Fillaux, C., Guillaumont, D., Moisy, P., Den Auwer, C.,...,Sánchez Marcos, E. (2010). Molecular solids of actinide hexacyanoferrate: Structure and bonding. IOP Conf. Series: Materials Science and Engineering, 012026(1)-012026(11).|