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Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms
Author(s) -
Carter Korey P.,
Kalaj Mark,
Surbella Robert G.,
Ducati Lucas C.,
Autschbach Jochen,
Cahill Christopher L.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702744
Subject(s) - uranyl , halogen bond , chemistry , halogen , polarizability , crystallography , terpyridine , atom (system on chip) , infrared spectroscopy , covalent bond , ligand (biochemistry) , density functional theory , raman spectroscopy , inorganic chemistry , computational chemistry , molecule , ion , organic chemistry , metal , biochemistry , alkyl , receptor , physics , optics , computer science , embedded system
Abstract Engaging the nominally terminal oxo atoms of the linear uranyl (UO 2 2+ ) 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.