title: A relativistic DFT probe of polypyrrolic macrocyclic diuranium(III) complexes with terminal solvents and iodines.
abstract: Relativistic density functional theory finds that two isomers of a diuranium(III) complex of a polypyrrolic macrocycle (H4L) feature active sites on uranium moieties, allowing for their potential application in activating industrially and economically important small molecules. To address this, a series of adducts [(X)nU2(L)]((2-m)+) (X = THF, I(-) and HI; n = 1 and 2; m = 0, 1 and 2) have been examined. The coordination from X to the exposed uranium(s) changes the general geometry and electronic structure slightly. Thermodynamic calculations reveal that iodine termination is energetically favored over THF/HI coordination. Graphical abstract Scalar and spin-orbit coupling relativistic DFT calculation reveals that the active sites on the uranium moieties of [U2(L)](2+) lead to formation of adducts [(THF)nU2(L)](2+), [InU2(L)]((2-n)+) and [(HI)nU2(L)](2+) (n = 1 and 2). Coordination to the exposed uranium(s) changes geometrical and electronic properties slightly, but iodine termination is the most energetically favored.
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: Dong-Mei
authors.initials: DM
authors.lastname: Su
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: Xiu-Jun
authors.initials: XJ
authors.lastname: Zheng
authors.affiliation: Key Laboratory of Bio-based Material Science and Technology of Education Ministry, College of Material Science and Engineering, Northeast Forestry University, Harbin, 150040, China. guoyrnefu@163.com.
authors.forename: Yuan-Ru
authors.initials: YR
authors.lastname: Guo
authors.affiliation: Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin, 150080, China. panqjitc@163.com.
authors.forename: Qing-Jiang
authors.initials: QJ
authors.lastname: Pan
keywords: Diuranium(III) complex; Electronic structure; Relativistic DFT; Thermodynamic reaction