Journal article
Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms
Chemistry : a European journal, Vol.23(61), pp.15355-15369
11/02/2017
DOI: 10.1002/chem.201702744
PMID: 28707416
Abstract
Engaging the nominally terminal oxo atoms of the linear uranyl (UO22+) cation in non‐covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non‐covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen‐donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5‐dihalobenzoic acid and aromatic, chelating N‐donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5‐dichloro‐ (25diClBA) and 2,5‐dibromobenzoic acid (25diBrBA) coupled with 2,2′‐bipyridine (bipy) (1 and 2), 1,10‐phenanthroline (phen) (3–5), 2,2′:6′,2′′‐terpyridine (terpy) (6–8), or 4′‐chloro‐2,2′:6′,2′′‐terpyridine (Cl‐terpy) (9–10), which have been characterized through single crystal X‐ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5‐diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms.
Halogen bonding: A family of uranyl hybrid materials was generated based on a combination of 2,5‐dihalobenzoic acid and aromatic, chelating N‐donor ligands and was characterized through single crystal X‐ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials.
Details
- Title: Subtitle
- Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms
- Creators
- Korey P Carter - The George Washington UniversityMark Kalaj - The George Washington UniversityRobert G Surbella - The George Washington UniversityLucas C Ducati - University of São PauloJochen Autschbach - State University of New YorkChristopher L Cahill - The George Washington University
- Resource Type
- Journal article
- Publication Details
- Chemistry : a European journal, Vol.23(61), pp.15355-15369
- DOI
- 10.1002/chem.201702744
- PMID
- 28707416
- NLM abbreviation
- Chemistry
- ISSN
- 0947-6539
- eISSN
- 1521-3765
- Number of pages
- 15
- Grant note
- Office of Science (DE-FG02-05ER15736; DE-SC0001136)
- Language
- English
- Date published
- 11/02/2017
- Academic Unit
- Chemistry
- Record Identifier
- 9984216694702771
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