Cargando…
Three-Dimensional Noncovalent Interaction Network within [NpO(2)Cl(4)](2–) Coordination Compounds: Influence on Thermochemical and Vibrational Properties
[Image: see text] Noncovalent interactions (NCIs) can influence the stability and chemical properties of pentavalent and hexavalent actinyl (AnO(2)(+/2+)) compounds. In this work, the impact of NCIs (actinyl–hydrogen and actinyl–cation interactions) on the enthalpy of formation (ΔH(f)) and vibration...
Autores principales: | , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10598792/ https://www.ncbi.nlm.nih.gov/pubmed/37816161 http://dx.doi.org/10.1021/acs.inorgchem.3c02502 |
_version_ | 1785125632891420672 |
---|---|
author | Rajapaksha, Harindu Benthin, Grant C. Kravchuk, Dmytro V. Lightfoot, Haley Mason, Sara E. Forbes, Tori Z. |
author_facet | Rajapaksha, Harindu Benthin, Grant C. Kravchuk, Dmytro V. Lightfoot, Haley Mason, Sara E. Forbes, Tori Z. |
author_sort | Rajapaksha, Harindu |
collection | PubMed |
description | [Image: see text] Noncovalent interactions (NCIs) can influence the stability and chemical properties of pentavalent and hexavalent actinyl (AnO(2)(+/2+)) compounds. In this work, the impact of NCIs (actinyl–hydrogen and actinyl–cation interactions) on the enthalpy of formation (ΔH(f)) and vibrational features was evaluated using Np(VI) tetrachloro compounds as the model system. We calculated the ΔH(f) values of these solid-state compounds through density functional theory+ thermodynamics (DFT+ T) and validated the results against experimental ΔH(f) values obtained through isothermal acid calorimetry. Three structural descriptors were evaluated to develop predictors for ΔH(f), finding a strong link between ΔH(f) and hydrogen bond energy (E(H)(total)) for neptunyl–hydrogen interactions and total electrostatic attraction energy (E(electrostatic)(total)) for neptunyl–cation interactions. Finally, we used Raman spectroscopy together with bond order analysis to probe Np=O bond perturbation due to NCIs. Our results showed a strong correlation between the degree of NCIs by axial oxygen and red-shifting of Np=O symmetrical stretch (ν(1)) wavenumbers and quantitatively demonstrated that NCIs can weaken the Np=O bond. These properties were then compared to those of related U(VI) and Np(V) phases to evaluate the effects of subtle differences in the NCIs and overall properties. In general, the outcomes of our study demonstrated the role of NCIs in stabilizing actinyl solid materials, which consequently governs their thermochemical behaviors and vibrational signatures. |
format | Online Article Text |
id | pubmed-10598792 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-105987922023-10-26 Three-Dimensional Noncovalent Interaction Network within [NpO(2)Cl(4)](2–) Coordination Compounds: Influence on Thermochemical and Vibrational Properties Rajapaksha, Harindu Benthin, Grant C. Kravchuk, Dmytro V. Lightfoot, Haley Mason, Sara E. Forbes, Tori Z. Inorg Chem [Image: see text] Noncovalent interactions (NCIs) can influence the stability and chemical properties of pentavalent and hexavalent actinyl (AnO(2)(+/2+)) compounds. In this work, the impact of NCIs (actinyl–hydrogen and actinyl–cation interactions) on the enthalpy of formation (ΔH(f)) and vibrational features was evaluated using Np(VI) tetrachloro compounds as the model system. We calculated the ΔH(f) values of these solid-state compounds through density functional theory+ thermodynamics (DFT+ T) and validated the results against experimental ΔH(f) values obtained through isothermal acid calorimetry. Three structural descriptors were evaluated to develop predictors for ΔH(f), finding a strong link between ΔH(f) and hydrogen bond energy (E(H)(total)) for neptunyl–hydrogen interactions and total electrostatic attraction energy (E(electrostatic)(total)) for neptunyl–cation interactions. Finally, we used Raman spectroscopy together with bond order analysis to probe Np=O bond perturbation due to NCIs. Our results showed a strong correlation between the degree of NCIs by axial oxygen and red-shifting of Np=O symmetrical stretch (ν(1)) wavenumbers and quantitatively demonstrated that NCIs can weaken the Np=O bond. These properties were then compared to those of related U(VI) and Np(V) phases to evaluate the effects of subtle differences in the NCIs and overall properties. In general, the outcomes of our study demonstrated the role of NCIs in stabilizing actinyl solid materials, which consequently governs their thermochemical behaviors and vibrational signatures. American Chemical Society 2023-10-10 /pmc/articles/PMC10598792/ /pubmed/37816161 http://dx.doi.org/10.1021/acs.inorgchem.3c02502 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Rajapaksha, Harindu Benthin, Grant C. Kravchuk, Dmytro V. Lightfoot, Haley Mason, Sara E. Forbes, Tori Z. Three-Dimensional Noncovalent Interaction Network within [NpO(2)Cl(4)](2–) Coordination Compounds: Influence on Thermochemical and Vibrational Properties |
title | Three-Dimensional
Noncovalent Interaction Network
within [NpO(2)Cl(4)](2–) Coordination
Compounds: Influence on Thermochemical and Vibrational Properties |
title_full | Three-Dimensional
Noncovalent Interaction Network
within [NpO(2)Cl(4)](2–) Coordination
Compounds: Influence on Thermochemical and Vibrational Properties |
title_fullStr | Three-Dimensional
Noncovalent Interaction Network
within [NpO(2)Cl(4)](2–) Coordination
Compounds: Influence on Thermochemical and Vibrational Properties |
title_full_unstemmed | Three-Dimensional
Noncovalent Interaction Network
within [NpO(2)Cl(4)](2–) Coordination
Compounds: Influence on Thermochemical and Vibrational Properties |
title_short | Three-Dimensional
Noncovalent Interaction Network
within [NpO(2)Cl(4)](2–) Coordination
Compounds: Influence on Thermochemical and Vibrational Properties |
title_sort | three-dimensional
noncovalent interaction network
within [npo(2)cl(4)](2–) coordination
compounds: influence on thermochemical and vibrational properties |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10598792/ https://www.ncbi.nlm.nih.gov/pubmed/37816161 http://dx.doi.org/10.1021/acs.inorgchem.3c02502 |
work_keys_str_mv | AT rajapakshaharindu threedimensionalnoncovalentinteractionnetworkwithinnpo2cl42coordinationcompoundsinfluenceonthermochemicalandvibrationalproperties AT benthingrantc threedimensionalnoncovalentinteractionnetworkwithinnpo2cl42coordinationcompoundsinfluenceonthermochemicalandvibrationalproperties AT kravchukdmytrov threedimensionalnoncovalentinteractionnetworkwithinnpo2cl42coordinationcompoundsinfluenceonthermochemicalandvibrationalproperties AT lightfoothaley threedimensionalnoncovalentinteractionnetworkwithinnpo2cl42coordinationcompoundsinfluenceonthermochemicalandvibrationalproperties AT masonsarae threedimensionalnoncovalentinteractionnetworkwithinnpo2cl42coordinationcompoundsinfluenceonthermochemicalandvibrationalproperties AT forbestoriz threedimensionalnoncovalentinteractionnetworkwithinnpo2cl42coordinationcompoundsinfluenceonthermochemicalandvibrationalproperties |