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

Autor(es)

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

Afiliação do(s) autor(es)

^[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

• Tipo de documento: Artigo Científico
• Fonte: CHEMISTRY-A EUROPEAN JOURNAL; v. 23, n. 61, p. 15355-15369, NOV 2 2017.
• Citações Web of Science: 17

Resumo

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)

• Processo FAPESP: 14/21930-9 - Estudo do efeito do solvente na constante de acoplamento 1JPt-Tl em complexos de metais pesados por dinâmica molecular ab initio
• Beneficiário: Lucas Colucci Ducati
• Modalidade de apoio: Bolsas no Exterior - Pesquisa