Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms

Author(s)

Carter, Korey P. ^[1] ; Kalaj, Mark ^[1] ; Surbella, III, Robert G. ; Ducati, Lucas C. ^[2] ; Autschbach, Jochen ^[3] ; Cahill, Christopher L. ^[4]

Affiliation

^[1] George Washington Univ, Dept Chem, 800 22nd St, NW, Washington, DC 20052 - USA

^[2] Univ Sao Paulo, Inst Chem, Dept Fundamental Chem, POB 26077, BR-05513970 Sao Paulo, SP - Brazil

^[3] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 - USA

^[4] Surbella, Robert G., III, George Washington Univ, Dept Chem, 800 22nd St, NW, Washington, DC 20052 - USA

• Document type: Journal article
• Source: CHEMISTRY-A EUROPEAN JOURNAL; v. 23, n. 61, p. 15355-15369, NOV 2 2017.
• Web of Science Citations: 17

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-dibromo-benzoic 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. (AU)

• FAPESP's process: 14/21930-9 - Study of the solvent effect on the spin spin coupling constant 1JPt-Tl in heavy metal complexes by ab initio molecular dynamics
• Grantee: Lucas Colucci Ducati
• Support Opportunities: Scholarships abroad - Research