Search

Traditional models of lanthanide electronic structure suggest that bonding is predominantly ionic, and that covalent orbital mixing is not an important factor in determining magnetic properties. Here, 4f orbital mixing and its impact on the magnetic susceptibility of Cp'3Eu (Cp' = C5H4SiMe3) was analyzed experimentally using magnetometry and X-ray absorption spectroscopy (XAS) methods at the C K-, Eu M5,4-, and L3-edges. Pre-edge features in the experimental and TDDFT-calculated C K-edge XAS spectra provided unequivocal evidence of C 2p and Eu 4f orbital mixing in the π-antibonding orbital of a' symmetry. The charge-transfer configurations resulting from 4f orbital mixing were identified spectroscopically by using Eu M5,4-edge and L3-edge XAS. Modeling of variable-temperature magnetic susceptibility data showed excellent agreement with the XAS results and indicated that increased magnetic susceptibility of Cp'3Eu is due to removal of the degeneracy of the 7F1 excited state due to mixing between the ligand and Eu 4f orbitals.

Targeted alpha therapy (TAT) pairs the specificity of antigen targeting with the lethality of alpha particles to eradicate cancerous cells. Actinium-225 [225Ac; t1/2 = 9.920(3) days] is an alpha-emitting radioisotope driving the next generation of TAT radiopharmaceuticals. Despite promising clinical results, a fundamental understanding of Ac coordination chemistry lags behind the rest of the Periodic Table due to its limited availability, lack of stable isotopes, and inadequate systems poised to probe the chemical behavior of this radionuclide. In this work, we demonstrate a platform that combines an 8-coordinate synthetic ligand and a mammalian protein to characterize the solution and solid-state behavior of the longest-lived Ac isotope, 227Ac [t1/2 = 21.772(3) years]. We expect these results to direct renewed efforts for 225Ac-TAT development, aid in understanding Ac coordination behavior relative to other +3 lanthanides and actinides, and more broadly inform this element's position on the Periodic Table.

In LnO2 (Ln = Ce, Pr, and Tb), the amount of Ln 4f mixing with O 2p orbitals was determined by O K-edge X-ray absorption near edge (XANES) spectroscopy and was similar to the amount of mixing between the Ln 5d and O 2p orbitals. This similarity was unexpected since the 4f orbitals are generally perceived to be "core-like" and can only weakly stabilize ligand orbitals through covalent interactions. While the degree of orbital mixing seems incompatible with this view, orbital mixing alone does not determine the degree of stabilization provided by a covalent interaction. We used a Hubbard model to determine this stabilization from the energies of the O 2p to 4f, 5d(eg), and 5d(t2g) excited charge-transfer states and the amount of excited state character mixed into the ground state, which was determined using Ln L3-edge and O K-edge XANES spectroscopy. The largest amount of stabilization due to mixing between the Ln 4f and O 2p orbitals was 1.6(1) eV in CeO2. While this energy is substantial, the stabilization provided by mixing between the Ln 5d and O 2p orbitals was an order of magnitude greater consistent with the perception that covalent bonding in the lanthanides is largely driven by the 5d orbitals rather than the 4f orbitals.

The reaction of 1 equiv of 1-azidoadamantane with [UIII(NR2)3] (R = SiMe3) in Et2O results in the formation of [UV(NR2)3(NAd)] (1, Ad = 1-adamantyl) in good yields. The electronic structure of 1, as well as those of the related U(V) complexes, [UV(NR2)3(NSiMe3)] (2) and [UV(NR2)3(O)] (3), were analyzed with EPR spectroscopy, SQUID magnetometry, NIR-visible spectroscopy, and crystal field modeling. This analysis revealed that, within this series of complexes, the steric bulk of the E2- (E═O, NR) ligand is the most important factor in determining the electronic structure. In particular, the increasing steric bulk of this ligand, on moving from O2- to [NAd]2-, results in increasing U═E distances and E-U-Namide angles. These changes have two principal effects on the resulting electronic structure: (1) the increasing U═E distances decreases the energy of the fσ orbital, which is primarily σ* with respect to the U═E bond, and (2) the increasing E-U-Namide angles increases the energy of fδ, due to increasing antibonding interactions with the amide ligands. As a result of the latter change, the electronic ground state for complexes 1 and 2 is primarily fφ in character, whereas the ground state for complex 3 is primarily fδ.

The reactivity of two metallocene aryloxide U(III) complexes, [(C5Me5)2U(O-Ar)], Ar = 4-tBuC6H4, 1; Ar = 2,6-tBu2-4-CH3C6H2(BHT), 3, with CO2and CS2has been investigated. The reaction of 1 with CO2produces a bridging oxo complex, [{(C5Me5)2(4-tBuC6H4-O)U}2(μ2-O)], 4, while 3 with CO2results in reductive disproportionation to form the bridging carbonate species, [{(C5Me5)2(BHT)U}2(μ2-κ2:η1-CO3)], 5. The difference in reactivity can be attributed to the steric properties of the ligand because the reaction of 3 with an oxo-delivering agent yields a U(V) terminal oxo complex, [(C5Me5)2(BHT)U═O], 6. Reduction of CS2to form a bridging (CS2)2-ligand, [{(C5Me5)2(tBuC6H4-O)U}2(μ2-CS2)], 7, is observed with 1, while the reaction of 3 with CS2also produces a bridging (CS2)2-reduced ligand complex, followed by C-H bond activation of a methyl group from one (C5Me5)1-ring, [(C5Me5)2(BHT)U{μ2-C(H)S2}U(C5Me4CH2)(C5Me5)(BHT)], 8. All compounds are characterized by NMR and IR spectroscopy, and their solid-state structures are determined by X-ray crystallography.

This study presents the role of 5d orbitals in the bonding, and electronic and magnetic structure of Ce imido and oxo complexes synthesized with a tris(hydroxylaminato) [((2- t BuNO)C6H4CH2)3N]3- (TriNO x 3-) ligand framework, including the reported synthesis and characterization of two new alkali metal-capped Ce oxo species. X-ray spectroscopy measurements reveal that the imido and oxo materials exhibit an intermediate valent ground state of the Ce, displaying hallmark features in the Ce LIII absorption of partial f-orbital occupancy that are relatively constant for all measured compounds. These spectra feature a double peak consistent with other formal Ce(iv) compounds. Magnetic susceptibility measurements reveal enhanced levels of temperature-independent paramagnetism (TIP). In contrast to systems with direct bonding to an aromatic ligand, no clear correlation between the level of TIP and f-orbital occupancy is observed. CASSCF calculations defy a conventional van Vleck explanation of the TIP, indicating a single-reference ground state with no low-lying triplet excited state, despite accurately predicting the measured values of f-orbital occupancy. The calculations do, however, predict strong 4f/5d hybridization. In fact, within these complexes, despite having similar f-orbital occupancies and therefore levels of 4f/5d hybridization, the d-state distributions vary depending on the bonding motif (Ce[double bond, length as m-dash]O vs. Ce[double bond, length as m-dash]N) of the complex, and can also be fine-tuned based on varying alkali metal cation capping species. This system therefore provides a platform for understanding the characteristic nature of Ce multiple bonds and potential impact that the associated d-state distribution may have on resulting reactivity.

Reaction of [K(DME)][Th{N(R)(SiMe2 CH2)}2(NR2)] (R = SiMe3) with 1 equiv. of [U(NR2)3(NH2)] (1) in THF, in the presence of 18-crown-6, results in formation of a bridged uranium-thorium nitride complex, [K(18-crown-6)(THF)2][(NR2)3UIV(μ-N)ThIV(NR2)3] (2), which can be isolated in 48% yield after work-up. Complex 2 is the first isolable molecular mixed-actinide nitride complex. Also formed in the reaction is the methylene-bridged mixed-actinide nitride, [K(18-crown-6)][K(18-crown-6)(Et2O)2][(NR2)2U(μ-N)(μ-κ2-C,N-CH2SiMe2NR)Th(NR2)2]2 (3), which can be isolated in 34% yield after work-up. Complex 3 is likely generated by deprotonation of a methyl group in 2 by [NR2]-, yielding the new μ-CH2 moiety and HNR2. Reaction of 2 with 0.5 equiv. of I2 results in formation of a UV/ThIV bridged nitride, [(NR2)3UV(μ-N)ThIV(NR2)3] (4), which can be isolated in 42% yield after work-up. The electronic structure of 4 was analyzed with EPR spectroscopy, SQUID magnetometry, and NIR-visible spectroscopy. This analysis demonstrated that the energies of 5f orbitals of 4 are largely determined by the strong ligand field exerted by the nitride ligand.

Spin-vibronic coupling leads to spin relaxation in paramagnetic molecules, and an understanding of factors that contribute to this phenomenon is essential for designing next-generation spintronics technology, including single-molecule magnets and spin-based qubits, wherein long-lifetime magnetic ground states are desired. We report spectroscopic and magnetic characterization of the isoelectronic and isostructural series of homoleptic zerovalent transition metal triad M(CNDipp)6 (M = V, Nb, Ta; CNDipp = 2,6-diisopropylphenyl isocyanide) and show experimentally the significant increase in spin relaxation rate upon going from V to Nb to Ta. Correlated electronic calculations and first principle spin-phonon computations support the role of spin-orbit coupling in modulating spin-phonon relaxation. Our results provide experimental evidence that increasing magnetic anisotropy through spin-orbit coupling interactions leads to increased spin-vibronic relaxation, which is detrimental to long spin lifetime in paramagnetic molecules.

We report the synthesis and characterization of the trinuclear 4d-4f compounds [Co(C5Me5)2][(C5Me5)2Ln(μ-S)2Mo(μ-S)2Ln(C5Me5)2], 1-Ln (Ln = Y, Gd, Tb, Dy), containing the highly polarizable MoS43- bridging unit. UV-Vis-NIR diffuse reflectance spectra and DFT calculations of 1-Ln reveal a low-energy metal-to-metal charge transfer transition assigned to charge transfer from the singly occupied 4dz2 orbital of MoV to the empty 5d orbitals of the lanthanides (4d in the case of 1-Y), mediated by sulfur-based 3p orbitals. Electron paramagnetic resonance spectra collected for 1-Y in a tetrahydrofuran solution show large 89Y hyperfine coupling constants of A⊥ = 23 MHz and A|| = 26 MHz, indicating the presence of significant yttrium-localized unpaired electron density. Magnetic susceptibility data support similar electron delocalization and ferromagnetic Ln-Mo exchange for 1-Gd, 1-Tb, and 1-Dy. This ferromagnetic exchange gives rise to an S = 15/2 ground state for 1-Gd and one of the largest magnetic exchange constants involving GdIII observed to date, with JGd-Mo = +16.1(2) cm-1. Additional characterization of 1-Tb and 1-Dy by ac magnetic susceptibility measurements reveals that both compounds exhibit slow magnetic relaxation. Although a Raman magnetic relaxation process is dominant for both 1-Tb and 1-Dy, an extracted thermal relaxation barrier of Ueff = 68 cm-1 for 1-Dy is the largest yet reported for a complex containing a paramagnetic 4d metal center. Together, these results provide a potentially generalizable route to enhanced nd-4f magnetic exchange, revealing opportunities for the design of new nd-4f single-molecule magnets and bulk magnetic materials.

We report the synthesis and characterization of the trinuclear 4d-4f compounds [Co(C5Me5)2][(C5Me5)2Ln(μ-S)2Mo(μ-S)2Ln(C5Me5)2], 1-Ln (Ln = Y, Gd, Tb, Dy), containing the highly polarizable MoS43- bridging unit. UV-Vis-NIR diffuse reflectance spectra and DFT calculations of 1-Ln reveal a low-energy metal-to-metal charge transfer transition assigned to charge transfer from the singly occupied 4dz2 orbital of MoV to the empty 5d orbitals of the lanthanides (4d in the case of 1-Y), mediated by sulfur-based 3p orbitals. Electron paramagnetic resonance spectra collected for 1-Y in a tetrahydrofuran solution show large 89Y hyperfine coupling constants of A⊥ = 23 MHz and A|| = 26 MHz, indicating the presence of significant yttrium-localized unpaired electron density. Magnetic susceptibility data support similar electron delocalization and ferromagnetic Ln-Mo exchange for 1-Gd, 1-Tb, and 1-Dy. This ferromagnetic exchange gives rise to an S = 15/2 ground state for 1-Gd and one of the largest magnetic exchange constants involving GdIII observed to date, with JGd-Mo = +16.1(2) cm-1. Additional characterization of 1-Tb and 1-Dy by ac magnetic susceptibility measurements reveals that both compounds exhibit slow magnetic relaxation. Although a Raman magnetic relaxation process is dominant for both 1-Tb and 1-Dy, an extracted thermal relaxation barrier of Ueff = 68 cm-1 for 1-Dy is the largest yet reported for a complex containing a paramagnetic 4d metal center. Together, these results provide a potentially generalizable route to enhanced nd-4f magnetic exchange, revealing opportunities for the design of new nd-4f single-molecule magnets and bulk magnetic materials.

Significant orbital mixing is rare in lanthanide complexes because of the limited radial extent of the 4f orbitals, which results in a generally small stabilization due to 4f orbital interactions. Nevertheless, even a small amount of additional stabilization could enhance lanthanide separations. One lanthanide complex in which orbital mixing has been extensively studied both experimentally and computationally is cerocene, COT2Ce, where COT is cyclooctatetraene. This compound has a singlet ground state with a low-lying, triplet excited state. Previous fluorescence studies on trimethylsilyl-substituted cerocenes indicate the triplet state is 0.4 eV higher in energy than the singlet state. In addition, computational studies predict that the triplet is 0.3 to 1 eV higher in energy than the singlet. The synthesis of highly pure COT2Ce by Walter and Andersen allowed its physical properties to be accurately measured. Using these measurements, we evaluate the stabilization of the 4f orbitals using two, independent approaches. A Hubbard model is used to evaluate the stabilization of the ground state due to orbital mixing. This stabilization, which is also the singlet-triplet gap, is -0.29 eV using this model. This gap was also from the temperature independent paramagnetism of COT2Ce, which yielded a value of -0.32 eV.

The spectrum of "Tc(V) gluoconate" in Figure 2d is inaccurate. This sample is contaminated with 25-50% pertechnetate as determined by EXAFS and XANES analysis, respectively. The error does not affect the conclusions of the manuscript.

Significant orbital mixing is rare in lanthanide complexes because of the limited radial extent of the 4f orbitals, which results in a generally small stabilization due to 4f orbital interactions. Nevertheless, even a small amount of additional stabilization could enhance lanthanide separations. One lanthanide complex in which orbital mixing has been extensively studied both experimentally and computationally is cerocene, COT2Ce, where COT is cyclooctatetraene. This compound has a singlet ground state with a low-lying, triplet excited state. Previous fluorescence studies on trimethylsilyl-substituted cerocenes indicate the triplet state is 0.4 eV higher in energy than the singlet state. In addition, computational studies predict that the triplet is 0.3 to 1 eV higher in energy than the singlet. The synthesis of highly pure COT2Ce by Walter and Andersen allowed its physical properties to be accurately measured. Using these measurements, we evaluate the stabilization of the 4f orbitals using two, independent approaches. A Hubbard model is used to evaluate the stabilization of the ground state due to orbital mixing. This stabilization, which is also the singlet-triplet gap, is -0.29 eV using this model. This gap was also from the temperature independent paramagnetism of COT2Ce, which yielded a value of -0.32 eV.

Technetium-99 (half-life of 2.1 × 105 yrs, βmax = 0.29 MeV) is a hazardous radiological contaminant, which, in its predominant form of pertechnetate (TcO4–), is highly mobile in the environment. Most strategies for the removal of pertechnetate from the environment involve uptake and/or absorption of pertechnetate using resins, clays, cationic metal-organic frameworks and even thorium borate ceramic like materials. Alternative approaches have involved the reduction and subsequent sequestration of lower valent technetium species using iron, sulfides, or iron sulfides. Our lab has explored this strategy using the lacunary alpha-2 Wells–Dawson polyoxometalate (α2-[P2W17O61]10–) to both reduce and sequester lower valent technetium, and we have reported on the ligand features that stabilize the reduced species. In this work we investigate the potential of “plenary” Keggin POMs (XW12O40n–) (X = P, Si, Al, n = 3, 4, 5, respectively) to both reduce TcO4– and stabilize the reduced Tc species. Specifically, we report on the mechanism by which the reduction of technetium occurs and find that PW12, SiW12, and AlW12 promote the reduction of TcO4– to lower valent states. X-ray absorption spectroscopy was used to confirm a combination of TcIV {in the form of TcO2·2H2O and Tc2(µ-O)24+} and TcV, which is subsequently complexed into a POM defect as a TcV=O species.

The anions pertechnetate, TcO4-, and perrhenate, ReO4-, exhibit very similar chemical and physical properties. Revealing and understanding disparities between them enhances fundamental understanding of both. Electrospray ionization generated the gas-phase proton bound dimer (TcO4-)(H+)(ReO4-). Collision induced dissociation of the dimer yielded predominantly HTcO4 and ReO4-, which according to Cooks' kinetic method indicates that the proton affinity (PA) of TcO4- is greater than that of ReO4-. Density functional theory computations agree with the experimental observation, providing PA[TcO4-] = 300.1 kcal mol-1 and PA[ReO4-] = 297.2 kcal mol-1. Attempts to rationalize these relative PAs based on elementary molecular parameters such as atomic charges indicate that the entirety of bond formation and concomitant bond disruption needs to be considered to understand the energies associated with such protonation processes. Although in both the gas and solution phases, TcO4- is a stronger base than ReO4-, it is noted that the significance of even such qualitative accordance is tempered by the very different natures of the underlying phenomena.

The anions pertechnetate, TcO4-, and perrhenate, ReO4-, exhibit very similar chemical and physical properties. Revealing and understanding disparities between them enhances fundamental understanding of both. Electrospray ionization generated the gas-phase proton bound dimer (TcO4-)(H+)(ReO4-). Collision induced dissociation of the dimer yielded predominantly HTcO4 and ReO4-, which according to Cooks' kinetic method indicates that the proton affinity (PA) of TcO4- is greater than that of ReO4-. Density functional theory computations agree with the experimental observation, providing PA[TcO4-] = 300.1 kcal mol-1 and PA[ReO4-] = 297.2 kcal mol-1. Attempts to rationalize these relative PAs based on elementary molecular parameters such as atomic charges indicate that the entirety of bond formation and concomitant bond disruption needs to be considered to understand the energies associated with such protonation processes. Although in both the gas and solution phases, TcO4- is a stronger base than ReO4-, it is noted that the significance of even such qualitative accordance is tempered by the very different natures of the underlying phenomena.

Understanding how interactions between the f orbitals and ligand orbitals in lanthanide and actinide systems affect their physical properties is the central issue in f-element chemistry. A wide variety of approaches including both theoretical and experimental tools have been used to study these relationships. Among the most widely used tools has been crystal field theory (CFT), which bridges theory and experiment in that it is a model based largely on atomic theory that is parametrized using experimental data. Crystal field theory is quite accurate for the lanthanides, due in part to the highly contracted nature of the 4f orbitals. For actinides, crystal field theory is less accurate, potentially due to the treatment of orbital mixing. In CFT, orbital mixing is handled implicitly by allowing the electron repulsion parameters (Slater Fk parameters) and the spin-orbit coupling constant to vary. As a result, orbital mixing in CFT is isotropic in that the Fk parameters and the spin-orbit coupling constant affect all f orbitals equally. This approximation works well for the lanthanides due to the limited degree of orbital mixing in these complexes. In actinide complexes, the 5f orbitals have greater overlap with the ligand orbitals, and this approximation is less accurate than in the lanthanides. Here, we report a modification of CFT that includes the effect of orbital mixing on electron repulsion and spin-orbit coupling for each f orbital. The model is applied to the tetravalent uranium hexahalide dianions and PrCl63- for which the energies of many low-lying excited states are known. The new model generally fits the data as well the traditional CFT although with fewer parameters. However, the new model does not fit the data better than the more complex CFT models of Faucher and co-workers. The results of the model show in detail how changes in overlap and orbital energies influence the energies of the bonding and antibonding orbitals.

Understanding how interactions between the f orbitals and ligand orbitals in lanthanide and actinide systems affect their physical properties is the central issue in f-element chemistry. A wide variety of approaches including both theoretical and experimental tools have been used to study these relationships. Among the most widely used tools has been crystal field theory (CFT), which bridges theory and experiment in that it is a model based largely on atomic theory that is parametrized using experimental data. Crystal field theory is quite accurate for the lanthanides, due in part to the highly contracted nature of the 4f orbitals. For actinides, crystal field theory is less accurate, potentially due to the treatment of orbital mixing. In CFT, orbital mixing is handled implicitly by allowing the electron repulsion parameters (Slater Fk parameters) and the spin-orbit coupling constant to vary. As a result, orbital mixing in CFT is isotropic in that the Fk parameters and the spin-orbit coupling constant affect all f orbitals equally. This approximation works well for the lanthanides due to the limited degree of orbital mixing in these complexes. In actinide complexes, the 5f orbitals have greater overlap with the ligand orbitals, and this approximation is less accurate than in the lanthanides. Here, we report a modification of CFT that includes the effect of orbital mixing on electron repulsion and spin-orbit coupling for each f orbital. The model is applied to the tetravalent uranium hexahalide dianions and PrCl63- for which the energies of many low-lying excited states are known. The new model generally fits the data as well the traditional CFT although with fewer parameters. However, the new model does not fit the data better than the more complex CFT models of Faucher and co-workers. The results of the model show in detail how changes in overlap and orbital energies influence the energies of the bonding and antibonding orbitals.

While preparing a follow-up manuscript, we found an error in one of the orbital reduction factors used in our crystal field models, given in Scheme 2. The third equation in that scheme was published as ka2t2 = 1 - 12 N2 2 a'p ; however, the correct formula is k a2t2 = 1 - 12 N'a'p2. (Table Presented).

Four simulated waste streams relevant to the vitrification of Hanford nuclear waste were studied to evaluate the removal kinetics of technetium-99 (Tc) and co-mingled Cr(VI) during treatment with solid ferrous hydroxide (Fe(OH)2(s)). Simulants treated with Fe(OH)2(s) were reacted for 24 h and sub-sampled periodically to monitor Tc and Cr removal. Solution sample analysis during the reaction was coupled with solid phase characterization, for example, X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD), to establish influence of the solid phase product on Tc and Cr removal rates. Based on these results, the majority of Tc and Cr removal occurs within the first 5 min of simulant contact with Fe(OH)2(s). However, the order in which Tc and Cr are completely removed from each simulant depends on the simulant chemistry, the preferred reduction pathway, and the solid phase product, for example, magnetite (Fe3O4) versus goethite (α-FeOOH). Low pH and low Cr concentrations favor rapid Tc removal, with XRD and XAS confirming that Fe3O4 readily incorporates reduced Tc(IV) into its structure. High pH, high Cr concentrations, and the presence of other co-mingled constituents favor heterogeneous removal of Tc early in the reaction (1 h, Tc removal slows as homogeneous removal of Cr begins to dominate, concurrent with an increase in the formation of FeOOH as the solid phase reaction product. These results suggest that for complex, high pH waste streams, Tc removal within the first hour after Fe(OH)2(s) treatment is necessary for complete Tc reduction and improved mineral immobilization.

The octadentate siderophore analog 3,4,3-LI(1,2-HOPO), denoted 343-HOPO hereafter, is known to have high affinity for both trivalent and tetravalent lanthanide and actinide cations. Here we extend its coordination chemistry to the rare-earth cations Sc3+ and Y3+ and characterize fundamental metal-chelator binding interactions in solution via UV-Vis spectrophotometry, nuclear magnetic resonance spectroscopy, and spectrofluorimetric metal-competition titrations, as well as in the solid-state via single crystal X-ray diffraction. Sc3+ and Y3+ binding with 343-HOPO is found to be robust, with both high thermodynamic stability and fast room temperature radiolabeling, indicating that 343-HOPO is likely a promising chelator for in vivo applications with both metals. As a proof of concept, we prepared a 86Y-343-HOPO complex for in vivo PET imaging, and the results presented herein highlight the potential of 343-HOPO chelated trivalent metal cations for therapeutic and theranostic applications.

Technetium-99, a prevalent by-product of the nuclear fuel cycle, is a transition metal with 9 accessible oxidation states and a half-life of 2.1 × 105 years. 99TcVII has been found in the environment surrounding National Lab sites and fuel reprocessing centers, and its separation and long-term storage is complicated by its extensive redox chemistry. In our prior work we have reported the synthesis and reduction of TcVO to TcIVO in α1- and α2-Wells–Dawson P2W17O6110– polyoxometalates and reported on the polyoxometalate features that promote reduction and stabilization. In this work we report on the oxidation state stabilization of TcVO, TcVIO and TcVIN within the α-Keggin PW11O397– polyoxometalate. Both Density Functional Theory and experimental results show that Tc in TBA4[TcVIN-PW11O39] can be reduced to TcV, but any subsequent electrons reduce the tungsten framework of the polyoxometalate. TBA4[TcVO-PW11O39] however, can be theoretically reduced down to TcI before reduction of the polyoxometalate occurs.

To extend organoactinide chemistry beyond uranium, reported here is the first structurally characterized transuranic hydrocarbyl complex, Np[η4 -Me2 NC(H)C6 H5 ]3 (1), from reaction of NpCl4 (DME)2 with four equivalents of K[Me2 NC(H)C6 H5 ]. Unlike the UIII species, the neptunium analogue can be used to access other NpIII complexes. The reaction of 1 with three equivalents of HE2 C(2,6-Mes2 -C6 H3 ) (E=O, S) yields [(2,6-Mes2 -C6 H3 )CE2 ]3 Np(THF)2 , maintaining the trivalent oxidation state.

The synthesis and characterization of U(iv) and Np(iv) selenium bis(phenolate) complexes are reported. The reaction of two equivalents of the U(iv) complex with p-benzoquinone results in the formation of a U(v)-U(v) species with a bridging reduced quinone. This represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex.

The synthesis and characterization of U(iv) and Np(iv) selenium bis(phenolate) complexes are reported. The reaction of two equivalents of the U(iv) complex with p-benzoquinone results in the formation of a U(v)-U(v) species with a bridging reduced quinone. This represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex.

The fission product, 99Tc, presents significant challenges to the long-term disposal of nuclear waste due to its long half-life, high fission yield, and to the environmental mobility of pertechnetate (TcO4-), the stable Tc species in aerobic environments. Migration of 99Tc from disposal sites can potentially be prevented by incorporating it into durable waste forms based on environmentally stable minerals. Since Tc(iv) and Fe(iii) have the same ionic radius, Tc(iv) can replace Fe(iii) in iron oxides. Environmentally durable iron oxides include goethite (α-FeOOH), hematite (α-Fe2O3), and magnesioferrite (MgFe2O4). The incorporation of Tc into two of these, hematite and magnesioferrite, as well as magnetite (Fe3O4) by means of simple, aqueous chemistry is presented starting from TcO4- in 5 M nitric acid. A combination of X-ray diffraction and X-ray absorption fine structure spectroscopy reveals that Tc(iv) replaces Fe(iii) within the iron oxide structures. Following incorporation, Tc doped samples were suspended in deionized water under aerobic conditions, and the release rates of Tc were determined. The results of this work show that Tc leaches more quickly from Fe3O4 than from α-Fe2O3 or MgFe2O4. Modeling the leach rates and comparison with the leach rate of Tc from TiO2 indicate that release of Tc is controlled by solid state diffusion.

Technetium contamination remains a major environmental problem at nuclear reprocessing sites, e.g., the Hanford Site, Washington, USA. At these sites, Tc is present in liquid waste destined for immobilization in a waste form or has been released into the subsurface environment. The high environmental risk associated with Tc is due to its long half-life (214 000 years) and the mobility of the oxidized anionic species Tc(VII)O4-. Under reducing conditions, TcO4- is readily reduced to Tc(IV), which commonly exists as a relatively insoluble and therefore immobile, hydrous Tc-oxide (TcO2·nH2O). The stability of Tc(IV) sequestered as solid phases depends on the solubility of the solid and susceptibility to reoxidation to TcO4-, which in turn depend on the (biogeo)chemical conditions of the environment and/or nuclear waste streams. Unfortunately, the solubility of crystalline TcO2 or amorphous TcO2·H2O is still above the maximum contaminant level (MCL) established by the U.S. EPA (900 pCi/L), and the kinetics of TcO2 oxidative dissolution can be on the order of days to years. In addition to oxygen, sulfur can form complexes that significantly affect the adsorption, solubility, and reoxidation potential of Tc, especially Tc(IV). The principal technetium sulfides are TcS2 and Tc2S7, but much less is known about the mechanisms of formation, stabilization, and reoxidation of Tc-sulfides. A common assumption is that sulfides are less soluble than their oxyhydrous counterparts. Determination of the molecular structure of Tc2S7 in particular has been hampered by the propensity of this phase to precipitate as an amorphous substance. Recent work indicates that the oxidation state of Tc in Tc2S7 is Tc(IV), in apparent contradiction to its nominal stoichiometry. Technetium is relatively immobile in reduced sediments and soils, but in many cases the exact sink for Tc has not been identified. Experiments and modeling have demonstrated that both abiotic and biologic mechanisms can exert strong controls on Tc mobility and that Tc binding or uptake into sulfide phases can occur. These and similar investigations also show that extended exposure to oxidizing conditions results in transformation of sulfide-stabilized Tc(IV) to a Tc(IV)O2-like phase without formation of measurable dissolved TcO4-, suggesting a solid-state transformation in which Tc(IV)-associated sulfide is preferentially oxidized before the Tc(IV) cation. This transformation of Tc(IV)-sulfides to Tc(IV)-oxides may be the main process that limits remobilization of Tc as Tc(VII)O4-. The efficacy of the final waste form to retain Tc also strongly depends on the ability of oxidizing species to enter the waste and convert Tc(IV) to Tc(VII). Many waste form designs are reducing (e.g., cementitious waste forms such as salt stone) and, therefore, attempt to restrict access of oxidizing species such that diffusion is the rate-limiting step in remobilization of Tc.

Understanding fundamental Tc chemistry is important to both the remediation of nuclear waste and the reprocessing of nuclear fuel; however, current knowledge of the electronic structure and spectral signatures of low-valent Tc compounds significantly lags behind the remainder of the d-block elements. In particular, identification and treatment of Tc speciation in legacy nuclear waste is challenging due to the lack of reference data especially for Tc compounds in the less common oxidation states (I-VI). In an effort to establish a spectroscopic library corresponding to the relevant conditions of extremely high ionic strength typical for the legacy nuclear waste, compounds with the general formula of [ fac-Tc(CO)3(OH2)3- n(OH) n]1- n (where n = 0-3) were examined by a range of spectroscopic techniques including 99Tc/13C NMR, IR, XPS, and XAS. In the series of monomeric aqua species, stepwise hydrolysis results in the increase of the Tc metal center electron density and corresponding progressive decrease of the Tc-C bond distances, Tc electron binding energies, and carbonyl stretching frequencies in the order [ fac-Tc(CO)3(OH2)3]+ > [ fac-Tc(CO)3(OH2)2(OH)] > [ fac-Tc(CO)3(OH2)(OH)2]-. These results correlate with established trends of the 99Tc upfield chemical shift and carbonyl 13C downfield chemical shift. The lone exception is [ fac-Tc(CO)3(OH)]4 which exhibits a comparatively low electron density at the metal center attributed to the μ3-bridging nature of the -OH ligands causing less σ-donation and no π-donation. This work also reports the first observations of these compounds by XPS and [ fac-Tc(CO)3Cl3]2- by XAS. The unique and distinguishable spectral features of the aqua [ fac-Tc(CO)3]+ complexes lay the foundation for their identification in the complex aqueous matrixes.

A cementitious waste form, Cast Stone, is a possible candidate technology for the immobilization of low activity nuclear waste (LAW) at the Hanford site. This work focuses on the addition of getter materials to Cast Stone that can sequester Tc from the LAW, and in turn, lower Tc release from the Cast Stone. Two getters which produce different products upon sequestering Tc from LAW were tested: Sn(II) apatite (Sn-A) that removes Tc as a Tc(IV)-oxide and potassium metal sulfide (KMS-2) that removes Tc as a Tc(IV)-sulfide species, allowing for a comparison of stability of the form of Tc upon entering the waste form. The Cast Stone with KMS-2 getter had the best performance with addition equivalent to ∼0.08wt% of the total waste form mass. The observed diffusion (Dobs) of Tc decreased from 4.6±0.2×10-12cm2/s for Cast Stone that did not contain a getter to 5.4±0.4×10-13cm2/s for KMS-2 containing Cast Stone. It was found that Tc-sulfide species are more stable against re-oxidation within getter containing Cast Stone compared with Tc-oxide and is the origin of the decrease in Tc Dobs when using the KMS-2.

Technetium-99 (Tc) is a problematic fission product that complicates the long-term disposal of nuclear waste due to its long half-life, high fission yield, and the environmental mobility of pertechnetate, its stable form in aerobic environments. One approach to preventing Tc contamination is through incorporation into durable waste forms based on weathering-resistant minerals such as rutile (titanium dioxide). Here, the incorporation of technetium into titanium dioxide by means of simple, aqueous chemistry - direct oxidation of titanium powder in the presence of ammonium fluoride - is achieved. X-ray absorption fine structure spectroscopy and diffuse reflectance spectroscopy indicate that Tc(IV) replaces Ti(IV) within the structure. Rather than being incorporated as isolated Tc(IV) ions, Tc is present as pairs of edge-sharing Tc(IV) octahedra similar to molecular Tc(IV) complexes such as [(H2EDTA)TcIV](μ-O)2. Technetium-doped TiO2 was suspended in deionized water under aerobic conditions, and the Tc leached under these conditions was followed for 8 months. The normalized release rate of Tc (LRTc) from the TiO2 particles is low (3 × 10-6 g m-2 d-1), which illustrates the potential utility of TiO2 as waste form. However, the small size of the as-prepared TiO2 nanoparticles results in an estimated retention of Tc of 104 years, which is only a fraction of the half-life of Tc (2.1 × 105 years).

Understanding the nature of covalent (band-like) vs ionic (atomic-like) electrons in metal oxides continues to be at the forefront of research in the physical sciences. In particular, the development of a coherent and quantitative model of bonding and electronic structure for the lanthanide dioxides, LnO2 (Ln = Ce, Pr, and Tb), has remained a considerable challenge for both experiment and theory. Herein, relative changes in mixing between the O 2p orbitals and the Ln 4f and 5d orbitals in LnO2 are evaluated quantitatively using O K-edge X-ray absorption spectroscopy (XAS) obtained with a scanning transmission X-ray microscope and density functional theory (DFT) calculations. For each LnO2, the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t2g (σ-bonding) and eg (π-bonding) symmetry. The remarkable agreement between experiment and theory also shows that significant mixing with the O 2p orbitals occurs in a band derived from the 4f orbitals of a2u symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO2 that is ascribed to a unique interaction derived from the 4f orbitals of t1u symmetry (σ- and π-bonding). O K-edge XAS and DFT results are compared with complementary L3-edge and M5,4-edge XAS measurements and configuration interaction calculations, which shows that each spectroscopic approach provides evidence for ground state O 2p and Ln 4f orbital mixing despite inducing very different core-hole potentials in the final state.

Technetium (99Tc) immobilization by doping into iron oxide mineral phases may alleviate the problems with Tc volatility during vitrification of nuclear waste. Because reduced Tc, Tc(IV), substitutes for Fe(III) in the crystal structure by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation of Fe oxide minerals, two Tc-incorporated Fe minerals (Tc-goethite and Tc-magnetite/maghemite) were prepared and tested for Tc retention in glass melt samples at temperatures between 600 and 1000 °C. After being cooled, the solid glass specimens prepared at different temperatures at 600, 800, and 1000 °C were analyzed for Tc oxidation state using Tc K-edge XANES. In most samples, Tc was partially (95%) oxidized to Tc(VII) at temperature above 800 °C. Tc retention in glass melt samples prepared using Tc-incorporated Fe minerals were slightly higher (∼10%) than in glass prepared using KTcO4 because of limited and delayed Tc volatilization.

Acetamide diethylphosphonate (AcPhos)-functionalized silica has been shown to have a high affinity for U(vi) in pH 2-3 nitric acid. Previous work with AcPhos-functionalized silica has focused on actinide and lanthanide extraction under various conditions, but has shown poor reproducibility in the functionalization process. For this work, four AcPhos-functionalized SBA-15 materials were synthesized and evaluated based on their U(vi) sorption capacity and their stability in nitric acid. Materials synthesized using pyridine as a basic catalyst were shown to form a greater fraction of polymeric structures at the silica surface, which correlated with higher structural integrity upon contact with acidic solutions. Single-pulse 31P and 1H NMR spectra of these materials show evidence of phosphonic acid groups, as well as hydrogen-bonding interactions either between ligands or with the silica surface. Additionally, these materials were found to have significantly higher U(vi) sorption capacities and Keq values than the materials synthesized without pyridine, most likely due to the ion-exchange properties of the phosphonic acid groups. The 31P-31P DQ-DRENAR NMR technique was used to compare the average strength of dipolar coupling interactions between phosphorus atoms for the four materials. Because the strength of dipolar coupling interactions depends on the number and proximity of neighboring spins, this technique provides information about the average density of ligands on the surface. The conventional functionalization procedure yielded materials with the lowest average surface ligand density, while those using extended reaction times and the pyridine base catalyst yielded materials with higher surface ligand densities.

Acetamide diethylphosphonate (AcPhos)-functionalized silica has been shown to have a high affinity for U(vi) in pH 2-3 nitric acid. Previous work with AcPhos-functionalized silica has focused on actinide and lanthanide extraction under various conditions, but has shown poor reproducibility in the functionalization process. For this work, four AcPhos-functionalized SBA-15 materials were synthesized and evaluated based on their U(vi) sorption capacity and their stability in nitric acid. Materials synthesized using pyridine as a basic catalyst were shown to form a greater fraction of polymeric structures at the silica surface, which correlated with higher structural integrity upon contact with acidic solutions. Single-pulse 31P and 1H NMR spectra of these materials show evidence of phosphonic acid groups, as well as hydrogen-bonding interactions either between ligands or with the silica surface. Additionally, these materials were found to have significantly higher U(vi) sorption capacities and Keq values than the materials synthesized without pyridine, most likely due to the ion-exchange properties of the phosphonic acid groups. The 31P-31P DQ-DRENAR NMR technique was used to compare the average strength of dipolar coupling interactions between phosphorus atoms for the four materials. Because the strength of dipolar coupling interactions depends on the number and proximity of neighboring spins, this technique provides information about the average density of ligands on the surface. The conventional functionalization procedure yielded materials with the lowest average surface ligand density, while those using extended reaction times and the pyridine base catalyst yielded materials with higher surface ligand densities.

Achieving magnetic remanence at single isolated metal sites dispersed at the surface of a solid matrix has been envisioned as a key step toward information storage and processing in the smallest unit of matter. Here, we show that isolated Dy(III) sites distributed at the surface of silica nanoparticles, prepared with a simple and scalable two-step process, show magnetic remanence and display a hysteresis loop open at liquid 4He temperature, in contrast to the molecular precursor which does not display any magnetic memory. This singular behavior is achieved through the controlled grafting of a tailored Dy(III) siloxide complex on partially dehydroxylated silica nanoparticles followed by thermal annealing. This approach allows control of the density and the structure of isolated, "bare" Dy(III) sites bound to the silica surface. During the process, all organic fragments are removed, leaving the surface as the sole ligand, promoting magnetic remanence.

Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher electronegativity of the Na atom, resulting in large distortions of the pertechnetate tetrahedron and deshielding of the 99Tc nucleus relative to the aqueous TcO4-. At the other extreme, the large Cs and Rb atoms interact only weakly with the pertechnetate, have closer to perfect tetrahedral symmetry at the Tc atom, and have very similar vibrational spectra, even though the crystal structure of CsTcO4 is orthorhombic while that of RbTcO4 is tetragonal. Further trends are observed in the cell volume and quadrupolar coupling constant.

Treatment and immobilization of technetium-99 (99Tc) contained in reprocessed nuclear waste and present in contaminated subsurface systems represents a major environmental challenge. One potential approach to managing this highly mobile and long-lived radionuclide is immobilization into micro- and meso-porous crystalline solids, specifically sodalite. We synthesized and characterized the structure of perrhenate sodalite, Na8[AlSiO4]6(ReO4)2, and the structure of a mixed guest perrhenate/pertechnetate sodalite, Na8[AlSiO4]6(ReO4)2-x(TcO4)x. Perrhenate was used as a chemical analogue for pertechnetate. Bulk analyses of each solid confirm a cubic sodalite-type structure (P4̅3n, No. 218 space group) with rhenium and technetium in the 7+ oxidation state. High-resolution nanometer scale characterization measurements provide first-of-a-kind evidence that the ReO4- anions are distributed in a periodic array in the sample, nanoscale clustering is not observed, and the ReO4- anion occupies the center of the sodalite β-cage in Na8[AlSiO4]6(ReO4)2. We also demonstrate, for the first time, that the TcO4- anion can be incorporated into the sodalite structure. Lastly, thermochemistry measurements for the perrhenate sodalite were used to estimate the thermochemistry of pertechnetate sodalite based on a relationship between ionic potential and the enthalpy and Gibbs free energy of formation for previously measured oxyanion-bearing feldspathoid phases. The results collected in this study suggest that micro- and mesoporous crystalline solids maybe viable candidates for the treatment and immobilization of 99Tc present in reprocessed nuclear waste streams and contaminated subsurface environments.

The synthesis and characterisation of a rare U(iii) alkyl complex, U[η4-Me2NC(H)C6H5]3, using the dimethylbenzylamine (DMBA) ligand has been accomplished. While attempting to prepare the U(iv) compound, reduction to the U(iii) complex occurred. In the analogous Th(iv) system, C-H bond activation of a methyl group of one dimethylamine was observed yielding Th[η4-Me2NC(H)C6H5]2[η5-(CH2)MeNC(H)C6H5] with a dianionic DMBA ligand. The utility of these complexes as starting materials has been analyzed using a bulky dithiocarboxylate ligand to yield tetravalent actinide species.

Technetium (99Tc) is a problematic fission product for the long-term disposal of nuclear waste due to its long half-life, high fission yield, and to the environmental mobility of pertechnetate, the stable species in aerobic environments. One approach to preventing 99Tc contamination is using sufficiently durable waste forms. We report the incorporation of technetium into a family of synthetic spinel ferrites that have environmentally durable natural analogs. A combination of X-ray diffraction, X-ray absorption fine structure spectroscopy, and chemical analysis reveals that Tc(IV) replaces Fe(III) in octahedral sites and illustrates how the resulting charge mismatch is balanced. When a large excess of divalent metal ions is present, the charge is predominantly balanced by substitution of Fe(III) by M(II). When a large excess of divalent metal ions is absent, the charge is largely balanced by creation of vacancies among the Fe(III) sites (maghemitization). In most samples, Tc is present in Tc-rich regions rather than being homogeneously distributed.

The synthesis and characterisation of a rare U(iii) alkyl complex, U[η4-Me2NC(H)C6H5]3, using the dimethylbenzylamine (DMBA) ligand has been accomplished. While attempting to prepare the U(iv) compound, reduction to the U(iii) complex occurred. In the analogous Th(iv) system, C-H bond activation of a methyl group of one dimethylamine was observed yielding Th[η4-Me2NC(H)C6H5]2[η5-(CH2)MeNC(H)C6H5] with a dianionic DMBA ligand. The utility of these complexes as starting materials has been analyzed using a bulky dithiocarboxylate ligand to yield tetravalent actinide species.

At the U.S. Department of Energy Hanford Site, Tc-99 is a component of low-activity waste (LAW) fractions of the nuclear tank waste and removal of Tc from LAW streams would greatly benefit the site remediation process. In this study, we investigated the removal of Tc(VII), as pertechnetate, from deionized water (DIW) and a LAW simulant through batch sorption testing and solid phase characterization using tin (II) apatite (Sn-A) and SnCl2. Sn-A showed higher levels of Tc removal from both DIW and LAW simulant. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/XEDS) and X-ray absorption spectroscopy (XAS) of reacted Sn-A in DIW showed that TcO4- is reduced to Tc(IV) on the Sn-A surface. The performance of Sn-A in the LAW simulant was lowered due to a combined effect of the high alkalinity, which lead to an increased dissolution of Sn from the Sn-A, and a preference for the reduction of Cr(VI).

A tetravalent cerium macrocyclic complex (CeLK4) was prepared with an octadentate terephthalamide ligand comprised of hard catecholate donors and characterized in the solution state by spectrophotometric titrations and electrochemistry and in the crystal by X-ray diffraction. The solution-state studies showed that L exhibits a remarkably high affinity toward Ce4+, with log β110 = 61(2) and ΔG = -348 kJ/mol, compared with log β110 = 32.02(2) for the analogous Pr3+ complex. In addition, L exhibits an unusual preference for forming CeL4- relative to formation of the analogous actinide complex, ThL4-, which has β110 = 53.7(5). The extreme stabilization of tetravalent cerium relative to its trivalent state is also evidenced by the shift of 1.91 V in the redox potential of the Ce3+/Ce4+ couple of the complex (measured at -0.454 V vs SHE). The unprecedented behavior prompted an electronic structure analysis using L3- and M5,4-edge X-ray absorption near-edge structure (XANES) spectroscopies and configuration interaction calculations, which showed that 4f-orbital bonding in CeLK4 has partial covalent character due to ligand-to-metal charge transfer (LMCT) in the ground state. The experimental results are presented in the context of earlier measurements on tetravalent cerium compounds, indicating that the amount of LMCT for CeLK4 is similar to that observed for [Et4N]2[CeCl6] and CeO2 and significantly less than that for the organometallic sandwich compound cerocene, (C8H8)2Ce. A simple model to rationalize changes in 4f orbital bonding for tri- and tetravalent lanthanide and actinide compounds is also provided.

Technetium ((99)Tc) is an abundant, long-lived radioactive fission product whose mobility in the subsurface is largely governed by its oxidation state. Tc immobilization is crucial for radioactive waste management and environmental remediation. Tc(IV) incorporation in spinels has been proposed as a novel method to increase Tc retention in glass waste forms during vitrification. However, experiments under high-temperature and oxic conditions show reoxidation of Tc(IV) to volatile pertechnetate, Tc(VII). Here we examine this problem with ab initio molecular dynamics simulations and propose that, at elevated temperatures, doping with first row transition metal can significantly enhance Tc retention in magnetite in the order Co>Zn>Ni. Experiments with doped spinels at 700 °C provide quantitative confirmation of the theoretical predictions in the same order. This work highlights the power of modern, state-of-the-art simulations to provide essential insights and generate theory-inspired design criteria of complex materials at elevated temperatures.

The electronic structure in the complete series of stable lanthanide sesquioxides, Ln2O3 (Ln = La to Lu, except radioactive Pm), has been evaluated using oxygen K-edge X-ray absorption spectroscopy (XAS) with a scanning transmission X-ray microscope (STXM). The experimental results agree with recent synthetic, spectroscopic and theoretical investigations that provided evidence for 5d orbital involvement in lanthanide bonding, while confirming the traditional viewpoint that there is little Ln 4f and O 2p orbital mixing. However, the results also showed that changes in the energy and occupancy of the 4f orbitals can impact Ln 5d and O 2p mixing, leading to several different bonding modes for seemingly identical Ln2O3 structures. On moving from left to right in the periodic table, abrupt changes were observed for the energy and intensity of transitions associated with Ln 5d and O 2p antibonding states. These changes in peak intensity, which were directly related to the amounts of O 2p and Ln 5d mixing, were closely correlated to the well-established trends in the chemical accessibility of the 4f orbitals towards oxidation or reduction. The unique insight provided by the O K-edge XAS is discussed in the context of several recent theoretical and physical studies on trivalent lanthanide compounds.

Many efforts have focused on the sequestration and immobilization of 99Tc because the radionuclide is highly mobile in oxidizing environments and presents serious health risks due to its radiotoxicity and long half-life (t1/2 = 213 000 a). One of the more common methods for Tc removal from solution and immobilization in solids is based on reducing Tc from highly soluble Tc(VII) to sparingly soluble Tc(IV). Here, we report results obtained with two potassium metal sulfides (KMS-2 and KMS-2-SS) that are capable of reducing Tc(VII) to Tc(IV). Batch sorption experiments were performed in both oxic and anoxic conditions for 15 d in both deionized water (DIW) and a highly caustic (pH ∼ 13.6), high ionic strength (8.0 mol L-1), low-activity waste (LAW) stream simulant solution. Tc removal for both materials in DIW is improved in anoxic conditions compared to oxic conditions as a result of a higher solution pH. In DIW and anoxic conditions, KMS-2 is capable of removing ∼45% of Tc, and KMS-2-SS is capable of removing ∼90% of Tc. Both materials perform even better in the LAW simulant and remove more than 90% of available Tc after 15 d of contact in anoxic conditions. Postreaction solids analyses indicate that Tc(VII) is reduced to Tc(IV) and that Tc(IV) is bonded to S atoms in a Tc2S7 complex. Examination of the materials after Tc removal by X-ray diffraction shows that the initially crystalline KMS-2 materials lose much of their initial long-range order. We suggest a Tc removal mechanism wherein the TcO4- enters the interlayer of the KMS-2 materials where it is reduced by sulfide, which results in a distorted crystalline structure and a solid-state Tc2S7 complex.

Lu[CH(SiMe3)2]3 reacts with [SiO2-700] to give [(≡SiO)Lu[CH(SiMe3)2]2] and CH2(SiMe3)2. [(≡SiO)Lu[CH(SiMe3)2]2] is characterized by solid-state NMR and EXAFS spectroscopy, which show that secondary Lu···C and Lu···O interactions, involving a γ-CH3 and a siloxane bridge, are present. From X-ray crystallographic analysis, the molecular analogues Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 0-2) also have secondary Lu···C interactions. The (1)H NMR spectrum of Lu[CH(SiMe3)2]3 shows that the -SiMe3 groups are equivalent to -125 °C and inequivalent below that temperature, ΔG(⧧)(Tc = 148 K) = 7.1 kcal mol(-1). Both -SiMe3 groups in Lu[CH(SiMe3)2]3 have (1)JCH = 117 ± 1 Hz at -140 °C. The solid-state (13)C CPMAS NMR spectrum at 20 °C shows three chemically inequivalent resonances in the area ratio of 4:1:1 (12:3:3); the J-resolved spectra for each resonance give (1)JCH = 117 ± 2 Hz. The (29)Si CPMAS NMR spectrum shows two chemically inequivalent resonances with different values of chemical shift anisotropy. Similar observations are obtained for Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 1 and 2). The spectroscopic data point to short Lu···Cγ contacts corresponding to 3c-2e Lu···Cγ-Siβ interactions, which are supported by DFT calculations. Calculated natural bond orbital (NBO) charges show that Cγ carries a negative charge, while Lu, Hγ, and Siβ carry positive charges; as the number of O-based ligands increases so does the positive charge at Lu, which in turns shortens the Lu···Cγ distance. The change in NBO charges and the resulting changes in the spectroscopic and crystallographic properties show how ligands and surface-support sites rearrange to accommodate these changes, consistent with Pauling's electroneutrality concept.

Metal-organic frameworks featuring pores lined with exposed metal cations have received attention for a wide range of adsorption-related applications. While many frameworks with coordinatively unsaturated M(II) centers have been reported, there are relatively few examples of porous materials with coordinatively unsaturated M(III) centers. Here, we report the synthesis and characterization of Ti3O(OEt)(bdc)3(solv)2 (Ti-MIL-101; bdc(2-) = 1,4-benzenedicarboxylate; solv = N,N-dimethylformamide, tetrahydrofuran), the first metal-organic framework containing exclusively Ti(III) centers. Through a combination of gas adsorption, X-ray diffraction, magnetic susceptibility, and electronic and vibrational spectroscopy measurements, this high-surface-area framework is shown to contain five-coordinate Ti(III) centers upon desolvation, which irreversibly bind O2 to form titanium(IV) superoxo and peroxo species. Electronic absorption spectra suggest that the five-coordinate Ti(III) sites adopt a distorted trigonal-bipyramidal geometry that effectively shields nuclear charge and inhibits strong adsorption of nonredox-active gases.