Electronic spectra of uranium tetrachloride clusters with electron-donor ligands

Komyak, A. I.; Zazhogin, A. P.; Umreiko, D. S.; Lugovsky, Anatoliy

doi:10.1007/s10812-009-9168-0

Cited by 5 publications

(4 citation statements)

References 17 publications

(17 reference statements)

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“…Thus, U 3+ (5f 3 ) in Sc 2 UN@C 80 and U 4+ (5f 2 ) in Sc 2 UC@C 80 possess the 4 I 9/2 and 3 H 4 Hund ground states, respectively. This phenomenon also occurs for f 2 in the O h and D 4 h crystal fields. , …”

Section: Resultsmentioning

confidence: 99%

“…This phenomenon also occurs for f 2 in the O h and D 4h crystal fields. 50,51 The analysis of FMOs is shown in Figure 4. Unpaired electrons are arranged in single occupied molecular orbitals (SOMO), including SOMO-1 for the open-shell triplet Sc 2 UC@I h (31924)-C 80 and an additional SOMO-2 for the quartet Sc 2 UN@I h (31924)-C 80 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc₂UX@I_h(31924)-C₈₀ (X = C, N)

Zhao

Yuan

et al. 2019

Inorg. Chem.

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Mixed-metal uranium-based endohedral clusterfullerenes, Sc2UX@C80 (X = C, N), which were recently reported in experiments, have been investigated considering heptagon-containing isomers by density functional theory calculations in conjunction with statistical thermodynamic analysis. The triplet Sc2UC@I h (31924)-C80 and quartet Sc2UN@I h (31924)-C80, named after the spiral number (31924), are found to be thermodynamically stable and satisfy aromaticity rules. Furthermore, the restricted movements of the Sc2UX (X = C, N) cluster in I h (31924)-C80 have been demonstrated via ab initio molecular dynamics simulations. The six-electron transfer from the inner cluster to the cage results in the electronic structures (Sc2UX)6+@C80 6– (X = C, N), which were also confirmed by natural bond orbital analysis. On the basis of the frontier molecular orbitals, the oxidation states of uranium in Sc2UC@C80 and Sc2UN@C80 are +IV and +III, respectively, with residual electrons in 5f orbitals of U. The chemical bond between U and C (N) of the inner cluster is characterized as a double bond (single bond) by an analysis of the Mayer bond orders. There are covalent interactions between the inner cluster and outer cage, which is clarified by the quantum theory of atoms in molecules. IR spectra of the optimal isomers have also been simulated, which show the clear difference between Sc2UX@C80 (X = C, N). These findings, together with simulated results, are expected to supply useful information in future experiments of mixed-metal uranium-based endohedral clusterfullerenes.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc₂UX@I_h(31924)-C₈₀ (X = C, N)

Zhao

Yuan

et al. 2019

Inorg. Chem.

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“…UV/vis/NIR spectra have been recorded for the tetravalent f element complexes 1 , 2 , and 4 (see Figure S45 in the SI) showing characteristic bands related to f - f transitions in the tetravalent uranium complex 2 − and intense and very broad ligand-to-metal charge-transfer (LMCT) bands for the tetravalent cerium complex 4 . − …”

Section: Resultsmentioning

confidence: 99%

Series of Tetravalent Actinide Amidinates: Structure Determination and Bonding Analysis

et al. 2020

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Two series of isostructural tetravalent actinide amidinates [AnX((S)-PEBA) 3 ] (An = Th, U, Np; X = Cl, N 3 ) bearing the chiral (S,S)-N,N′-bis(1-phenylethyl)benzamidinate ((S)-PEBA) ligand have been synthesized and thoroughly characterized in solid and in solution. This study expands the already reported tetravalent neptunium complexes to the lighter actinides thorium and uranium. Furthermore, a rare Ce(IV) amidinate [CeCl((S)-PEBA) 3 ] was synthesized to compare its properties to those of the analogous tetravalent actinide complexes. All compounds were characterized in the solid state using singlecrystal XRD and infrared spectroscopy and in solution using NMR spectroscopy. Quantum chemical bonding analysis including also the isostructural Pa and Pu complexes was used to characterize the covalent contributions to any bond involving the metal cation. Th shows the least covalent character throughout the series, even substantially smaller than for the Ce complex. For U, Np, and Pu, similar covalent bonding contributions are found, but a natural population analysis reveals different origins. The 6d participation is the highest for U and decreases afterward, whereas the 5f participation increases continuously from Pa to Pu.

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“…In addition to these charge transfer transitions, the weaker intra 5f absorptions in the visible and near infra-red centered at 643, 1042 and 1103 nm are observed in concentrated solutions; these are characteristic of U 4+ ions and remain unshifted with respect to the parent UCl 4 in donating solvents. 31,32 In fluid solution at room temperature, excitation into each of the absorption bands (220-380 nm) affords luminescence spectra that comprise three broad featureless transitions centred at 415, 430 and 520 nm (Fig. 4).…”

Section: Solid State Structure Of [U(do3a)(dmso) 2 ]Brmentioning

confidence: 99%

The first structural and spectroscopic study of a paramagnetic 5f DO3A complex

Natrajan

2012

Dalton Trans.

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A 5f(2) uranium(IV) complex of the macrocycle DO3A (DO3A = [4,7,10-tris-carboxymethyl-,1,4,7,10-tetraaza-cyclododec-1-yl]-acetic acid) has been prepared and characterised in the solid state and in solution. The DO3A scaffold containing no strongly absorbing chromophores enables the facile detection of relatively long-lived (8-13 ns) UV-visible emission that possesses significant charge transfer character tentatively assigned to deactivation of the excited (3)F(2) 5f(1) 6d(1) electronic configuration. This study demonstrates, for the first time, that luminescence of simple U(iv) chelates is detectable in the absence of an antenna, potentially serving as a diagnostic tract for environmental U(IV) species.

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Electronic spectra of uranium tetrachloride clusters with electron-donor ligands

Cited by 5 publications

References 17 publications

In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc₂UX@I_h(31924)-C₈₀ (X = C, N)

In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc₂UX@I_h(31924)-C₈₀ (X = C, N)

Series of Tetravalent Actinide Amidinates: Structure Determination and Bonding Analysis

The first structural and spectroscopic study of a paramagnetic 5f DO3A complex

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Electronic spectra of uranium tetrachloride clusters with electron-donor ligands

Cited by 5 publications

References 17 publications

In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc2UX@Ih(31924)-C80 (X = C, N)

In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc2UX@Ih(31924)-C80 (X = C, N)

Series of Tetravalent Actinide Amidinates: Structure Determination and Bonding Analysis

The first structural and spectroscopic study of a paramagnetic 5f DO3A complex

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In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc₂UX@I_h(31924)-C₈₀ (X = C, N)

In-Depth Theoretical Probe into Novel Mixed-Metal Uranium-Based Endohedral Clusterfullerenes Sc₂UX@I_h(31924)-C₈₀ (X = C, N)