| Autor: |
Cary SK; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA., Galley SS; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA., Marsh ML; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA., Hobart DL; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA., Baumbach RE; National High Magnetic Field Laboratory, 1800 East Paul Dirac Drive, Tallahassee, Florida, 32310, USA., Cross JN; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA., Stritzinger JT; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA., Polinski MJ; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA., Maron L; Laboratoire de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquées, 31077 Toulouse Cedex 4, France., Albrecht-Schmitt TE; Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, Florida 32306, USA.; National High Magnetic Field Laboratory, 1800 East Paul Dirac Drive, Tallahassee, Florida, 32310, USA. |
| Abstrakt: |
Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent Pu III /Pu IV solid-state compound, Pu 3 (DPA) 5 (H 2 O) 2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure Pu III and Pu IV dipicolinate complexes, [Pu III (DPA)(H 2 O) 4 ]Br and Pu IV (DPA) 2 (H 2 O) 3 ·3H 2 O, as well as by a second mixed-valent compound, Pu III [Pu IV (DPA) 3 H 0.5 ] 2 , that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu 3 (DPA) 5 (H 2 O) 2 and in the IVCT. |
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