Incipient class II mixed valency in a plutonium solid-state compound

bibtex: ISI:000408323300008 bibtex\location:'MACMILLAN BUILDING, 4 CRINAN ST, LONDON N1 9XW, ENGLAND',publisher:'NATURE PUBLISHING GROUP',type:'Article',affiliation:'Albrecht-Schmitt, TE (Reprint Author), Florida State Univ, Dept Chem & Biochem, 95 Chieftan Way, Tallahassee, FL 32306 USA. Albrecht-Schmitt, TE (Reprint Author), Natl High Magnet Field Lab, 1800 East Paul Dirac Dr, Tallahassee, FL 32310 USA. Maron, L (Reprint Author), Inst Natl Sci Appl, Lab Phys & Chim Nanoobjets, F-31077 Toulouse 4, France. Cary, Samantha K.; Galley, Shane S.; Marsh, Matthew L.; Hobart, David L.; Cross, Justin N.; Stritzinger, Jared T.; Polinski, Matthew J.; Albrecht-Schmitt, Thomas E., Florida State Univ, Dept Chem & Biochem, 95 Chieftan Way, Tallahassee, FL 32306 USA. Baumbach, Ryan E.; Albrecht-Schmitt, Thomas E., Natl High Magnet Field Lab, 1800 East Paul Dirac Dr, Tallahassee, FL 32310 USA. Maron, Laurent, Inst Natl Sci Appl, Lab Phys & Chim Nanoobjets, F-31077 Toulouse 4, France.','author-email':'[email protected] [email protected]',da:'2018-12-05','doc-delivery-number':'FE6MJ',eissn:'1755-4349','funding-acknowledgement':'US Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program [DE-FG02-13ER16414]; National Science Foundation [DMR-1157490]; State of Florida; US Department of Energy','funding-text':'This material is based upon work supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program under award number DE-FG02-13ER16414. We are especially grateful for the assistance and supervision by the Office of Environmental Health and Safety at Florida State University, specifically J. A. Johnson and A. L. Gray of the Office of Radiation Safety for their facilitation of these studies. Magnetization measurements using the VSM SQUID MPMS were performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative agreement number DMR-1157490, the State of Florida, and the US Department of Energy. We are grateful for helpful discussions with N. M. Edelstein, M. P. Jensen and G. Liu.','journal-iso':'Nat. Chem.','keywords-plus':'MOLECULAR-ORBITAL METHODS; BASIS-SETS; COMPLEXES; ACTINIDE; EUROPIUM; ENERGY; PSEUDOPOTENTIALS; ELEMENT; CALIFORNIUM; CHLORIDES','number-of-cited-references':'42','research-areas':'Chemistry','times-cited':'5','unique-id':'ISI:000408323300008','usage-count-last-180-days':'12','usage-count-since-2013':'21','web-of-science-categories':'Chemistry, Multidisciplinary'\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)(H2O)(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)(H2O)(4)] Br and Pu-IV(DPA)(2)(H2O)(3)center dot 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)(H2O)(2) and in the IVCT

Giant coercivity and high magnetic blocking temperatures for N2 3− radical-bridged dilanthanide complexes upon ligand dissociation

Single-molecule magnets typically only retain information in the presence of an applied magnetic field and at very low temperatures. Here, Demir, Long and co-workers design N2 3– radical-bridged dilanthanide complexes that exhibit giant coercivities and 100-s magnetic blocking temperatures of up to 20 K