A set of self-assembled tri- and tetrapodal metal coordination cage structures (cage-1 and cage-2, respectively) constructed from the uranyl dication (UO22+) and a dibenzoic acid functionalised cis-calix[4]pyrrole (1) are described. The inherent photochemical reactivity of the uranyl dication mediates the transformation of cage-1 to cage-2via the activation of molecular oxygen.
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| http://dx.doi.org/10.1039/c8cc05160g | DOI Listing |
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Controlled and sequential single-electron reduction of the uranyl dication.
Dalton Trans
October 2024
EaStCHEM School of Chemistry, Joseph Black Building, University of Edinburgh, Edinburgh EH9 3FJ, UK.
A flexible tripodal pyrrole-imine ligand (HL) has been used to facilitate the controlled and sequential single-electron reductions of the uranyl dication from the U(VI) oxidation state to U(V) and further to U(IV), processes that are important to understanding the reduction of uranyl and its environmental remediation. The uranyl(VI) complexes UO(HL)(sol) (sol = THF, py) were straightforwardly accessed by the transamination reaction of HL with UO{N(SiMe)}(THF) and adopt 'hangman' structures in which one of the pyrrole-imine arms is pendant. While deprotonation of this arm by LiN(SiMe) causes no change in uranyl oxidation state, single-electron reduction of uranyl(VI) to uranyl(V) occurred on addition of two equivalents of KN(SiMe) to UO(HL)(sol).
View Article and Find Full Text PDFThe aqueous uranyl dication has long been known to facilitate the UV light-induced decomposition of aqueous VOCs (volatile organic compounds), the long-lived highly efficient, uranyl excited state. The lower-energy visible light excited uranyl ion is also able to cleave unactivated hydrocarbon C-H bonds, yet the development of this reactivity into controlled and catalytic C-H bond functionalization is still in its infancy, with almost all studies still focused on uranyl nitrate as the precatalyst. Here, hydrocarbon-soluble uranyl nitrate and chloride complexes supported by substituted phenanthroline (Phphen) ligands are compared to each other, and to the parent salts, as photocatalysts for the functionalization of cyclooctane by H atom abstraction.
View Article and Find Full Text PDFSynthesis, Isolation, and Study of Heterobimetallic Uranyl Crown Ether Complexes.
J Am Chem Soc
April 2024
Department of Chemistry, University of Kansas, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
Although crown ethers can selectively bind many metal cations, little is known regarding the solution properties of crown ether complexes of the uranyl dication, UO. Here, the synthesis and characterization of isolable complexes in which the uranyl dication is bound in an 18-crown-6-like moiety are reported. A tailored macrocyclic ligand, templated with a Pt(II) center, captures UO in the crown moiety, as demonstrated by results from single-crystal X-ray diffraction analysis.
View Article and Find Full Text PDFSystematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride.
Inorg Chem
March 2024
Department of Chemistry, The George Washington University, 800 22nd Street, NW, Washington, District of Columbia 20052, United States.
Reported are the syntheses, structural characterizations, and luminescence properties of three novel [UOCl] bearing compounds containing substituted 1,1'-dialkyl-4,4'-bipyridinum dications (i.e., viologens).
View Article and Find Full Text PDFA theoretical investigation of uranyl covalency symmetry-preserving excited state structures.
Phys Chem Chem Phys
November 2022
Department of Chemistry, Faraday Building, Lancaster University, Lancaster, LA1 4YB, UK.
Time dependent density functional theory (TDDFT) calculations have been performed on a series of symmetry-preserving excited states of the uranyl dication, UO. The simulated excited state electronic structures are compared to that of the ground state at both ground and excited state-optimised geometries. For the first time, the Quantum Theory of Atoms in Molecules (QTAIM) has been applied to the excited states electronic structures of uranyl in order to quantify the variation in bond covalency upon electronic excitation.
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