We report the synthesis and characterization of a new family of pentavalent uranyl amide complexes, supported also by photoluminescence and theoretical investigations. These studies reveal for the first time that the UV-visible emission of uranyl(V) is an admixture of charge transfer transitions accompanied by vibronic coupling of the quartet excited state with uranyl oxo and amide vibrations, thereby offering new insights into the electronic structure of the reactive uranyl(V)

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We report the preparation of a range of alkali metal uranyl(VI) tri- bis(silyl)amide complexes [{M(THF) x}{(μ-O)U(O)(N″)3}] (1M) (N″ = {N(SiMe3)2}-, M = Li, Na, x = 2; M = K, x = 3; M = K, Rb, Cs, x = 0) containing electrostatic alkali metal uranyl-oxo interactions. Reaction of 1M with 2,2,2-cryptand or 2 equiv of the appropriate crown ether resulted in the isolation of the separated ion pair species [U(O)2(N″)3][M(2,2,2-cryptand)] (3M, M = Li-Cs) and [U(O)2(N″)3][M(crown)2] (4M, M = Li, crown = 12-crown-4 ether; M = Na-Cs, crown = 15-crown-5 ether). A combination of crystallographic studies and IR, Raman and UV-vis spectroscopies has revealed that the 1M series adopts contact ion pair motifs in the solid state where the alkali metal caps one of the uranyl-oxo groups. Upon dissolution in THF solution, this contact is lost, and instead, separated ion pair motifs are observed, which is confirmed by the isolation of [U(O)2(N″)3][M(THF) n] (2M) (M = Li, n = 4; M = Na, K, n = 6). The compounds have been characterized by single crystal X-ray diffraction, multinuclear NMR spectroscopy, IR, Raman, and UV-vis spectroscopies, and elemental analyses.