title: Series of uranyl-4,4'-biphenyldicarboxylates and an occurrence of a cation-cation interaction: hydrothermal synthesis and in situ Raman studies.
abstract: Three uranium(VI)-bearing materials were synthesized hydrothermally using the organic ligand 4,4'-biphenyldicarboxylic acid: (UO2)(C14O4H8) (1); [(UO2)2(C14O4H8)2(OH)]·(NH4)(H2O) (2); (UO2)2(C14O4H8)(OH)2 (3). Compound 1 was formed after 1 day at 180 °C in an acidic environment (pH(i) = 4.03), and compounds 2 and 3 coformed after 3 days under basic conditions (pH(i) = 7.95). Coformation of all three compounds was observed at higher pH(i) (9.00). Ex situ Raman spectra of single crystals of 1-3 were collected and analyzed for signature peaks. In situ hydrothermal Raman data were also obtained and compared to the ex situ Raman spectra of the title compounds in an effort to acquire formation mechanism details. At pH(i) = 4.00, the formation of 1 was suggested by in situ Raman spectra. At an increased pH(i) (7.90), the in situ data implied the formation of compounds 1 and 3. The most basic conditions (pH(i) = 9.00) yielded a complex mixture of phases consistent with that of increased uranyl hydrolysis.
authors.affiliation: Department of Chemistry, The George Washington University, 725 21st Street NW, Washington, DC 20052, United States.
authors.forename: Paula M
authors.initials: PM
authors.lastname: Cantos
authors.forename: Laurent J
authors.initials: LJ
authors.lastname: Jouffret
authors.forename: Richard E
authors.initials: RE
authors.lastname: Wilson
authors.forename: Peter C
authors.initials: PC
authors.lastname: Burns
authors.forename: Christopher L
authors.initials: CL
authors.lastname: Cahill
mesh_terms: D001713:Biphenyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D002412:Cations / Q000737:chemistry; D003998:Dicarboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013059:Spectrum Analysis, Raman; D013696:Temperature; D014501:Uranium / Q000737:chemistry*
chemical_list: C535263:4,4'-biphenyldicarboxylic acid; D001713:Biphenyl Compounds; D002412:Cations; D003998:Dicarboxylic Acids; D014501:Uranium