Thermochemical properties of U(VI) hybrid materials containing uranyl tetrachloride anions

Cahill, Christopher L.; Deifel, Nicholas P.; Reusser, Dana; Zhang, Lei; Navrotsky, Alexandra

doi:10.1016/j.jct.2017.05.009

Cited by 8 publications

(22 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…23 Results from this study showed a significant shift in ΔH f for compounds with uranyl−cation interactions compared to those with uranyl−hydrogen interactions, but they were unable to correlate intermolecular interactions to changes in ΔH f due to limited data and similarities in structural topologies within uranyl−hydrogen systems. 23 This lack of experimental data prevents more indepth analysis of the relationship between the stability of these structures and the strength of these NCIs within the solid-state lattice. Additionally, efforts will further be needed to understand related Np and Pu systems to provide added insights into the electronic structure of f-block elements.…”

Section: Introductionmentioning

confidence: 61%

“…As the NCI network within uranyl hybrid materials can impact the optical properties of the materials, they are also likely to have impacts on their thermodynamics and overall formation energies (Δ H f ). To the best of our knowledge, only one study by Cahill et al evaluated the influence NCIs have on the value of Δ H f for hybrid materials containing the [UO 2 Cl 4 ] 2– anion . Results from this study showed a significant shift in Δ H f for compounds with uranyl–cation interactions compared to those with uranyl–hydrogen interactions, but they were unable to correlate intermolecular interactions to changes in Δ H f due to limited data and similarities in structural topologies within uranyl–hydrogen systems .…”

Section: Introductionmentioning

confidence: 79%

“…Experimental formation enthalpies for uranyl–cation and uranyl–hydrogen systems have previously been calculated through isothermal acid solution calorimetry. 23 Through this method, formation enthalpy reactions do not reference the system back to the standard states of each atom, but instead, values are calculated through the reaction performed to create each uranyl hybrid ( Table 4 ). Because of this, a DFT + thermodynamics approach was used to calculate the formation enthalpies to match the reactions from experiment and directly relate their values.…”

Section: Resultsmentioning

confidence: 99%

“…To the best of our knowledge, only one study by Cahill et al evaluated the influence NCIs have on the value of Δ H f for hybrid materials containing the [UO 2 Cl 4 ] 2– anion . Results from this study showed a significant shift in Δ H f for compounds with uranyl–cation interactions compared to those with uranyl–hydrogen interactions, but they were unable to correlate intermolecular interactions to changes in Δ H f due to limited data and similarities in structural topologies within uranyl–hydrogen systems . This lack of experimental data prevents more in-depth analysis of the relationship between the stability of these structures and the strength of these NCIs within the solid-state lattice.…”

Section: Introductionmentioning

confidence: 85%

See 3 more Smart Citations

Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

et al. 2022

View full text Add to dashboard Cite

Solid-state uranyl hybrid structures are often formed through unique intermolecular interactions occurring between a molecular uranyl anion and a charge-balancing cation. In this work, solid-state structures of the uranyl tetrachloride anion engaged in uranyl–cation and uranyl–hydrogen interactions were studied using density functional theory (DFT). As most first-principles methods used for systems of this type focus primarily on the molecular structure, we present an extensive benchmarking study to understand the methods needed to accurately model the geometric properties of these systems. From there, the electronic and vibrational structures of the compounds were investigated through projected density of states and phonon analysis and compared to the experiment. Lastly, we present a DFT + thermodynamics approach to calculate the formation enthalpies (ΔH f) of these systems to directly relate to experimental values. Through this methodology, we were able to accurately capture trends observed in experimental results and saw good quantitative agreement in predicted ΔH f compared to the value calculated through referencing each structure to its standard state. Overall, results from this work will be used for future combined experimental and computational studies on both uranyl and neptunyl hybrid structures to delineate how varying intermolecular interaction strengths relates to the overall values of ΔH f.

show abstract

Section: Introductionmentioning

confidence: 61%

Section: Introductionmentioning

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 85%

See 2 more Smart Citations

Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Solid-state uranyl (U(VI)O 2 2+ ) chloride compounds have been widely used to evaluate fundamental f-block chemistry and intermolecular interactions within actinide coordination compounds. 1−6 Most uranyl chloride solid phases are synthesized through evaporation of U(VI) in an acidic chloride media, which typically leads to the formation of the [UO 2 Cl 4 ] 2− coordination compounds. 1,4 Currently, there are 112 structures containing the [UO 2 Cl 4 ] 2− anions in the CCDC database.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Density Functional Theory Investigation of the Solid-State [UO₂Cl₄(H₂O)]^2– Complex

Rajapaksha,

Mason,

Forbes

2023

Inorg. Chem.

View full text Add to dashboard Cite

A significant number of solid-state [UO 2 Cl 4 ] 2− coordination compounds have been synthesized and structurally characterized. Yet, despite their purposive relative abundance in aqueous solutions, characterization of aquachlorouranium(VI) complexes remain rare. In the current study, a solid-state uranyl aqua chloro complex ((C 4 H 12 N 2 ) 2 [UO 2 Cl 4 (H 2 O)]Cl 2 ) was synthesized using piperazinium as a charge-balancing ligand, and the structure was determined using single-crystal X-ray diffraction. Using periodic density functional theory, the electronic structure of the [UO 2 Cl 4 (H 2 O)] 2− complex was compared to [UO 2 Cl 4 ] 2− to uncover the strengthening of the U�O bond in [UO 2 Cl 4 (H 2 O)] 2− . Changes in the strength of the U�O bond were validated further with Raman and IR spectroscopy, where uranyl symmetrical (ν 1 ) and asymmetrical (ν 3 ) stretches were blue-shifted compared to the reference [UO 2 Cl 4 ] 2− complex. Furthermore, the formation energy of the solid-state (C 4 H 12 N 2 ) 2 [UO 2 Cl 4 (H 2 O)]Cl 2 complex was calculated to be −287.60 ± 1.75 kJ mol −1 using isothermal acid calorimetry. The demonstrated higher stability relative to the related [UO 2 Cl 4 ] 2− complex was related to the relative stoichiometry of the counterions.

show abstract

Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System

et al. 2023

View full text Add to dashboard Cite

Together with the synthesis and experimental characterization of 14 hybrid materials containing [UO 2 X 4 ] 2À (X = Cl À and Br À ) and organic cations, we report on novel methods for determining correlation trends in their formation enthalpy (ΔH f ) and observed vibrational signatures. ΔH f values were analyzed through isothermal acid calorimetry and a Density Functional Theory + Thermodynamics (DFT + T) approach with results showing good agreement between theory and experiment. Three factors (packing efficiency, cation protonation enthalpy, and hydrogen bonding energy [ E total H;norm ]) were assessed as descriptors for trends in ΔH f . Results demonstrated a strong correlation between E total H;norm and ΔH f , highlighting the importance of hydrogen bonding networks in determining the relative stability of solid-state hybrid materials. Lastly, we investigate how hydrogen bonding networks affect the vibrational characteristics of uranyl solid-state materials using experimental Raman and IR spectroscopy and theoretical bond orders and find that hydrogen bonding can red-shift U�O stretching modes. Overall, the tightly integrated experimental and theoretical studies presented here bridge the trends in macroscopic thermodynamic energies and spectroscopic features with molecular-level details of the geometry and electronic structure. This modeling framework forms a basis for exploring 3D hydrogen bonding as a tunable design feature in the pursuit of supramolecular materials by rational design.

show abstract

Thermochemical properties of U(VI) hybrid materials containing uranyl tetrachloride anions

Cited by 8 publications

References 20 publications

Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

Synthesis, Characterization, and Density Functional Theory Investigation of the Solid-State [UO₂Cl₄(H₂O)]^2– Complex

Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System

Contact Info

Product

Resources

About

Thermochemical properties of U(VI) hybrid materials containing uranyl tetrachloride anions

Cited by 8 publications

References 20 publications

Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses

Synthesis, Characterization, and Density Functional Theory Investigation of the Solid-State [UO2Cl4(H2O)]2– Complex

Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System

Contact Info

Product

Resources

About

Synthesis, Characterization, and Density Functional Theory Investigation of the Solid-State [UO₂Cl₄(H₂O)]^2– Complex