Uranyl-Promoted Peroxide Generation: Synthesis and Characterization of Three Uranyl Peroxo [(UO2)2(O2)] Complexes

• Published in: Inorganic chemistry Vol. 54; no. 9; pp. 4208 - 4221
• Main Authors: Thangavelu, Sonia G, Cahill, Christopher L
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.05.2015; American Chemical Society (ACS)
• Subjects: Diffraction; Dimers; Ligands; Luminescence; Molecular structure; nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly); Peroxides; Synthesis; X-rays
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic502767k

Three novel uranyl­(VI) peroxide complexes, [(UO2)2(CH3COO)2­(O2)­(C10H8N2)] (1), [(UO2)2(CH3COO)2­(O2)­(C12H12N2)] (2), and [(UO2)3(CH3COO)4­(O2)­(C15H11N3)2] (3), have been synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and luminescence spectroscopy. Each of these structures feature a [(UO2)2(O2)] dimer with additional coordination by acetate, 2,2′-bipyridine (BPY), 5,5′-dimethyl-2,2′-bipyridine (MeBPY), or 2,2′:6,2″-terpyridine (TPY). Compound 3 consists of an additional uranyl unit functionalized with a TPY donor ligand. The presence of the peroxo ligand in 1–3 is due to in situ generation of peroxide when preparative solutions of 1–3 were exposed to ambient light and/or sunlight.