Synthesis of a Uranyl Persulfide Complex and Quantum Chemical Studies of Formation and Topologies of Hypothetical Uranyl Persulfide Cage Clusters

The compound Na₄[(UO₂)­(S₂)₃]­(CH₃OH)₈ was synthesized at room temperature in an oxygen-free environment. It contains a rare example of the [(UO₂)­(S₂)₃]^4– complex in which a uranyl ion is coordinated by three bidentate persulfide groups. We examined the possible linkage of these units to form nanoscale cage clusters analogous to those formed from uranyl peroxide polyhedra. Quantum chemical calculations at the density functional and multiconfigurational wave function levels show that the uranyl–persulfide–uranyl, U–(S₂)–U, dihedral angles of model clusters are bent due to partial covalent interactions. We propose that this bent interaction will favor assembly of uranyl ions through persulfide bridges into curved structures, potentially similar to the family of nanoscale cage clusters built from uranyl peroxide polyhedra. However, the U–(S₂)–U dihedral angles predicted for several model structures may be too tight for them to self-assemble into cage clusters with fullerene topologies in the absence of other uranyl-ion bridges that adopt a flatter configuration. Assembly of species such as [(UO₂)­(S₂)­(SH)₄]^4– or [(UO₂)­(S₂)­(C₂O₄)₄]^4– into fullerene topologies with ∼60 vertices may be favored by use of large counterions

Synthesis of a Uranyl Persulfide Complex and Quantum Chemical Studies of Formation and Topologies of Hypothetical Uranyl Persulfide Cage Clusters

The compound Na₄[(UO₂)­(S₂)₃]­(CH₃OH)₈ was synthesized at room temperature in an oxygen-free environment. It contains a rare example of the [(UO₂)­(S₂)₃]^4– complex in which a uranyl ion is coordinated by three bidentate persulfide groups. We examined the possible linkage of these units to form nanoscale cage clusters analogous to those formed from uranyl peroxide polyhedra. Quantum chemical calculations at the density functional and multiconfigurational wave function levels show that the uranyl–persulfide–uranyl, U–(S₂)–U, dihedral angles of model clusters are bent due to partial covalent interactions. We propose that this bent interaction will favor assembly of uranyl ions through persulfide bridges into curved structures, potentially similar to the family of nanoscale cage clusters built from uranyl peroxide polyhedra. However, the U–(S₂)–U dihedral angles predicted for several model structures may be too tight for them to self-assemble into cage clusters with fullerene topologies in the absence of other uranyl-ion bridges that adopt a flatter configuration. Assembly of species such as [(UO₂)­(S₂)­(SH)₄]^4– or [(UO₂)­(S₂)­(C₂O₄)₄]^4– into fullerene topologies with ∼60 vertices may be favored by use of large counterions

Raman Spectroscopic and ESI-MS Characterization of Uranyl Peroxide Cage Clusters

Strategies for interpreting mass spectrometric and Raman spectroscopic data have been developed to study the structure and reactivity of uranyl peroxide cage clusters in aqueous solution. We demonstrate the efficacy of these methods using the three best-characterized uranyl peroxide clusters, {U₂₄}, {U₂₈}, and {U₆₀}. Specifically, we show a correlation between uranyl–peroxo–uranyl dihedral bond angles and the position of the Raman band of the symmetric stretching mode of the peroxo ligand, develop methods for the assignment of the ESI mass spectra of uranyl peroxide cage clusters, and show that these methods are generally applicable for detecting these clusters in the solid state and solution and for extracting information about their bonding and composition without crystallization

Cation–Cation Interactions between Neptunyl(VI) Units

The boric acid flux reaction of NpO₂(ClO₄)₂ with NaClO₄ affords Na­[(NpO₂)₄B₁₅O₂₄(OH)₅(H₂O)]­(ClO₄)·0.75H₂O (<b>NaNpBO-1</b>). <b>NaNpBO-1</b> possesses a layered structure consisting of double neptunyl­(VI) borate sheets bridged by another Np^VI site through cation–cation interactions. The sole presence of Np^VI in <b>NaNpBO-1</b> is supported by absorption and vibrational spectroscopy

Cation–Cation Interactions between Neptunyl(VI) Units

The boric acid flux reaction of NpO₂(ClO₄)₂ with NaClO₄ affords Na­[(NpO₂)₄B₁₅O₂₄(OH)₅(H₂O)]­(ClO₄)·0.75H₂O (<b>NaNpBO-1</b>). <b>NaNpBO-1</b> possesses a layered structure consisting of double neptunyl­(VI) borate sheets bridged by another Np^VI site through cation–cation interactions. The sole presence of Np^VI in <b>NaNpBO-1</b> is supported by absorption and vibrational spectroscopy

Systematic Evolution from Uranyl(VI) Phosphites to Uranium(IV) Phosphates

Six new uranium phosphites, phosphates, and mixed phosphate–phosphite compounds were hydrothermally synthesized, with an additional uranyl phosphite synthesized at room temperature. These compounds can contain U^VI or U^IV, and two are mixed-valent U^VI/U^IV compounds. There appears to be a strong correlation between the starting pH and reaction duration and the products that form. In general, phosphites are more likely to form at shorter reaction times, while phosphates form at extended reaction times. Additionally, reduction of uranium from U^VI to U^IV happens much more readily at lower pH and can be slowed with an increase in the initial pH of the reaction mixture. Here we explore the in situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and alkali-metal carbonates. The resulting products reveal the evolution of compounds formed as these hydrothermal redox reactions proceed forward with time

Systematic Evolution from Uranyl(VI) Phosphites to Uranium(IV) Phosphates

Six new uranium phosphites, phosphates, and mixed phosphate–phosphite compounds were hydrothermally synthesized, with an additional uranyl phosphite synthesized at room temperature. These compounds can contain U^VI or U^IV, and two are mixed-valent U^VI/U^IV compounds. There appears to be a strong correlation between the starting pH and reaction duration and the products that form. In general, phosphites are more likely to form at shorter reaction times, while phosphates form at extended reaction times. Additionally, reduction of uranium from U^VI to U^IV happens much more readily at lower pH and can be slowed with an increase in the initial pH of the reaction mixture. Here we explore the in situ hydrothermal redox reactions of uranyl nitrate with phosphorous acid and alkali-metal carbonates. The resulting products reveal the evolution of compounds formed as these hydrothermal redox reactions proceed forward with time