title: Construction of Uranyl Organic Hybrids by Phosphonate and in Situ Generated Carboxyphosphonate Ligands.
abstract: The hydrothermal reaction of uranyl ions with (5-methyl-1,3-phenylene)diphosphonic acid (H4MPDP) in the presence of additives such as nitric acid, N-bearing species, and heterometal ions yielded five new uranyl organic hybrids: (H3O)[(UO2)5(H2O)4(H3DPB)2(H2DPB)(HDPB)]·2H2O (1), (Hphen)(phen)[(UO2)3(H2DPB)(HDPB)] (2), (H2dipy)[(UO2)3(MPDP)2] (3), Zn(bipy)(UO2)(MPDP) (4), and Co(bipy)(UO2)(MPDP)·H2O (5) (H5DPB = 3,5-diphosphonobenzoic acid; phen = 1,10-phenanthroline; dipy = 4,4'-bipyridine; bipy = 2,2'-bipyridine). Single-crystal X-ray diffraction (XRD) demonstrates that 1 and 2 are 3D frameworks constructed of uranyl centers and carboxyphosphonate DPB ligands; the latter were formed via the in situ oxidation of H4MPDP. In the homometallic uranyl diphosphonate 3, less common UO6square bipyramids connected by MPDP ligands were incorporated to form the 2D assembly. A further introduction of heterometal ions produced two heterobimetallic uranyl phosphonates 4 and 5. Both of them show layered structures, formed by UO6square bipyramids linked by MPDP ligands with heterometal-centered polyhedra decorated on the sides of the layers. It is found that the pH and heterometal ions have significant effects on the structures of the complexes. In addition to the syntheses and XRD characterization, the spectroscopic properties of these uranyl complexes were also addressed. To complement the experimental results, density functional theory calculations were carried out on several model complexes that feature a homo- or heterobimetallic molecular skeleton. Geometrical/electronic structures, IR spectra, and electronic absorptions were discussed.
authors.affiliation: State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street, Changchun, Jilin 130022, P. R. China.|University of Chinese Academy of Sciences , Beijing 100049, China.
authors.forename: Chao
authors.initials: C
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street, Changchun, Jilin 130022, P. R. China.
authors.forename: Weiting
authors.initials: W
authors.lastname: Yang
authors.affiliation: Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University , Harbin 150080, China.
authors.forename: Ning
authors.initials: N
authors.lastname: Qu
authors.affiliation: State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street, Changchun, Jilin 130022, P. R. China.
authors.forename: Lei-Jiao
authors.initials: LJ
authors.lastname: Li
authors.affiliation: Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University , Harbin 150080, China.
authors.forename: Qing-Jiang
authors.initials: QJ
authors.lastname: Pan
authors.affiliation: State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street, Changchun, Jilin 130022, P. R. China.
authors.forename: Zhong-Ming
authors.identifier: http://orcid.org/0000-0003-2894-6327
authors.initials: ZM
authors.lastname: Sun