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

Harindu Rajapaksha; Logan J. Augustine; Sara E. Mason; Tori Z. Forbes

doi:10.1002/anie.202305073

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

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

Harindu Rajapaksha, Logan J. Augustine, Sara E. Mason and Tori Z. Forbes

Angewandte Chemie (International ed.), Vol.62(33), pp.e202305073-n/a

08/14/2023

DOI: 10.1002/anie.202305073

PMID: 37177866

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Abstract

Together with the synthesis and experimental characterization of 14 hybrid materials containing [UO2X4]2− (X=Cl− and Br−) and organic cations, we report on novel methods for determining correlation trends in their formation enthalpy (ΔHf) and observed vibrational signatures. ΔHf 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 [ EH,normtotal ${{E}_{H,{\rm { norm}}}^{{\rm { total}}}$ ]) were assessed as descriptors for trends in ΔHf. Results demonstrated a strong correlation between EH,normtotal ${E_{{\rm{H}},{\rm{norm}}}^{{\rm{total}}} }$ and ΔHf, 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. Uranyl tetrahalide supramolecular systems are investigated using both experiment and Density Functional Theory. We intend to investigate the effect that hydrogen bonding may have on the formation enthalpies of these systems. Here, we demonstrate that an expanded network of hydrogen bonds can stabilize supramolecular complexes and directly affect their formation enthalpies.

Crystal Engineering

Hybrid Materials

Hydrogen Bonding

Periodic Density Functional Theory

UIOWA OA Agreement

Details

Title: Subtitle: Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System
Creators: Harindu Rajapaksha - University of Iowa
Logan J. Augustine - University of Iowa
Sara E. Mason - University of Iowa, Chemistry
Tori Z. Forbes - University of Iowa, Chemistry
Resource Type: Journal article
Publication Details: Angewandte Chemie (International ed.), Vol.62(33), pp.e202305073-n/a
DOI: 10.1002/anie.202305073
PMID: 37177866
NLM abbreviation: Angew Chem Int Ed Engl
ISSN: 1433-7851
eISSN: 1521-3773
Publisher: Wiley
Number of pages: 10
Grant note: DOI: 10.13039/100000015, name: U.S. Department of Energy, award: DE-SC0021420, DE-SC0012704
Language: English
Date published: 08/14/2023
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984449949902771

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