Actinide Structural Chemistry
Solution and solid-state structural chemistry plays an important role in our understanding of the chemical behavior of the actinides. In fact, recent work has shown that our limited understanding of actinide speciation continues to thwart efforts to reliably and predictably control the behavior of these elements under chemically complex conditions. To address this need, we have established a synthetic program focused on elucidating the effects of both inner- and outer- coordination sphere interactions on the formation, stability, and reactivity of actinide complexes and clusters. Beyond establishing structural systematics in these systems, we are also examining the correlation between solution species and those complexes observed in the solid-state. Such work is expected to provide fundamental insight into actinide bonding, periodicity, and reactivity of relevance to the long-term storage of spent nuclear fuel, waste management, and environmental mobility.
This work is supported by the Department of Energy Early Career Research Program
Relevant Publications
Blanes Díaz, A.; Stewart, O.; Vasiliu, M.; Nicholas, A.; Murray, A. V; Shore, M. C.; Dixon, D. A.; Knope, K. E*. Th(IV) Bromide Complexes: A Homoleptic Aqua Ion and a Novel Th(H2O)4Br4 Structural Unit. Cryst. Growth Des. 2022, 22(7), 4375-4381. https://doi.org/10.1021/acs.cgd.2c00353.
Wacker JN, Ditter AS, Cary SK, Murray AV, Bertke JA, Seidler GT, Kozimor SA, Knope KE.* Reactivity of a Chloride Decorated, Mixed Valent CeIII/IV38-Oxo Cluster. Inorganic Chemistry. 2022, 61(1), 193-205. DOI: 10.1021/acs.inorgchem.1c02705.
MacInnes M, Jones Z, Anderson N, Eiroa-Lledo C, Knope KE; Livshits M, Kozimor S, Mocko V, Rein F, Stein B, Wacker J. Molten Salts to Probe Outer-Coordination Sphere Effects on Lanthanide(III)/(II) Electron-Transfer Reactions. Dalton Transactions 2021, 50, 15696-15710. DOI: 10.1039/D1DT02708E.
Wacker JN; Nicholas AD; Vasiliu M; Marwitz AC; Bertke JA; Dixon DA; Knope KE.* Impact of Noncovalent Interactions on the Structural Chemistry of Thorium(IV)–Aquo–Chloro Complexes. Inorganic Chemistry, 2021, 60, 9, 6375-6390. DOI: 10.1021/acs.inorgchem.1c00099.
Murray AV, Wacker JN, Bertke JA, Knope KE.* Synthesis, Characterization, and Solid-State Structural Chemistry of Uranium(IV) Aliphatic Dicarboxylates. Crystal Growth & Design, 2021, 21, 4, 2429-2444. DOI: 10.1021/acs.cgd.1c00042.
Vanagas NA, Higgins RF, Wacker JN, Asuigui DRC, Warzecha E, Kozimor SA, Stoll SL, Schelter EJ, Bertke JA, Knope KE*. Mononuclear to Polynuclear U(IV) Structural Units: Effects of Reaction Conditions on U-Furoate Phase Formation. Chemistry – A European Journal, 2020, 26(26), 5872. DOI: 10.1002/chem.201905759
Wacker JN, Vasiliu M, Colliard I, Ayscue RL, Han SY, Bertke JA, Nyman M, Dixon DA, Knope KE*. Monomeric and Trimeric Thorium Chlorides Isolated from Acidic Aqueous Solution. Inorganic Chemistry, 2019, 58 (16), 10871-10882. DOI: 10.1021/acs.inorgchem.9b01238
Wacker JN, Han SY, Murray AV, Vanagas NA, Bertke JA, Sperling JM, Surbella RG, Knope KE*. From Thorium to Plutonium: Trends in Actinide(IV) Chloride Structural Chemistry. Inorganic Chemistry, 2019, 58(16), 10528-10591. DOI: 10.1021/acs.inorgchem.9b01279. Invited contribution to Forum Issue “Celebrating the Year of the Periodic Table: Emerging Investigators in Inorganic Chemistry.”