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Title: Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms

Abstract

The syntheses and crystal structures of six new complexes containing the UO 2 2+ cation, m ‐ or p ‐halobenzoic acid ligands (where halogens are Cl and I), and the chelating N‐donors 1,10‐phenanthroline (phen) ( 1 , 3 , 4 , and 6 ) or 2,2′:6′,2′′‐terpyridine (terpy) ( 7 and 9 ) are described and compared to UO 2 ‐ m ‐bromo‐ and p ‐bromobenzoic analogues ( 2 , 5 , and 8 ) that have been reported previously. The spectroscopic properties (both vibrational and luminescence) for all nine complexes along with stretching and interaction force constants are reported and redshifts are noted as the electron‐donating ability of the chelating N‐donors increases. Single crystal X‐ray diffraction analysis of these complexes shows that whereas inclusion of a chelating ligand (i.e. phen or terpy) in the uranyl first coordination sphere is important for limiting tecton diversity, variation of the position and identity of the halogen atom on the benzoic acid ligand exert much greater influence in terms of driving halogen bonding interactions with the uranyl oxo atoms. In particular, the polarizability of the selected halogen atom is shown to be the most important criterion for engineering oxo atom participation in noncovalent assembly.more » Spectroscopic analysis of complexes 1 – 9 , however, demonstrates that vibrational spectra are impacted most by the degree of electron donation by equatorial N‐donor ligands, and that in some cases, such donation may also facilitate oxo interactions with otherwise unfavorable halogen bond donors.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Department of Chemistry The George Washington University 800 22nd Street, NW 20052 Washington D.C. USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1379988
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Name: European Journal of Inorganic Chemistry Journal Volume: 2017 Journal Issue: 40; Journal ID: ISSN 1434-1948
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Kalaj, Mark, Carter, Korey P., and Cahill, Christopher L. Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms. Germany: N. p., 2017. Web. doi:10.1002/ejic.201700788.
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Kalaj, Mark, Carter, Korey P., & Cahill, Christopher L. Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms. Germany. https://doi.org/10.1002/ejic.201700788
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Kalaj, Mark, Carter, Korey P., and Cahill, Christopher L. Thu . "Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms". Germany. https://doi.org/10.1002/ejic.201700788.
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@article{osti_1379988,
title = {Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms},
author = {Kalaj, Mark and Carter, Korey P. and Cahill, Christopher L.},
abstractNote = {The syntheses and crystal structures of six new complexes containing the UO 2 2+ cation, m ‐ or p ‐halobenzoic acid ligands (where halogens are Cl and I), and the chelating N‐donors 1,10‐phenanthroline (phen) ( 1 , 3 , 4 , and 6 ) or 2,2′:6′,2′′‐terpyridine (terpy) ( 7 and 9 ) are described and compared to UO 2 ‐ m ‐bromo‐ and p ‐bromobenzoic analogues ( 2 , 5 , and 8 ) that have been reported previously. The spectroscopic properties (both vibrational and luminescence) for all nine complexes along with stretching and interaction force constants are reported and redshifts are noted as the electron‐donating ability of the chelating N‐donors increases. Single crystal X‐ray diffraction analysis of these complexes shows that whereas inclusion of a chelating ligand (i.e. phen or terpy) in the uranyl first coordination sphere is important for limiting tecton diversity, variation of the position and identity of the halogen atom on the benzoic acid ligand exert much greater influence in terms of driving halogen bonding interactions with the uranyl oxo atoms. In particular, the polarizability of the selected halogen atom is shown to be the most important criterion for engineering oxo atom participation in noncovalent assembly. Spectroscopic analysis of complexes 1 – 9 , however, demonstrates that vibrational spectra are impacted most by the degree of electron donation by equatorial N‐donor ligands, and that in some cases, such donation may also facilitate oxo interactions with otherwise unfavorable halogen bond donors.},
doi = {10.1002/ejic.201700788},
journal = {European Journal of Inorganic Chemistry},
number = 40,
volume = 2017,
place = {Germany},
year = {Thu Sep 07 00:00:00 EDT 2017},
month = {Thu Sep 07 00:00:00 EDT 2017}
}
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https://doi.org/10.1002/ejic.201700788
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