Ab Initio Investigation of the Na3[Ln(ODA)3]·2NaClO4·6H2O (Ln = Ce–Yb; ODA = Oxydiacetate) Series

Connolly, Blake J. P.; Lian, James Y. J.; Bernhardt, Paul V.; Riley, Mark J.

doi:10.1021/acs.inorgchem.2c01764

Cited by 3 publications

(2 citation statements)

References 70 publications

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“…The results of the point group analysis are compiled in Table 1. Comparing these results to the symmetry of Ln(ODA)3 molecular structures (Q'') by Connolly et al 67 we find their structure to be of perfect D3 symmetry, with σSym(Q'', D3) = 0.00 for all their eight complexes (See Tables S3 and S4). The trivalent neodymium(III) ion has an electronic configuration [Xe]4f 3 .…”

Section: Molecular Structuresupporting

confidence: 63%

“…66 A recent ab initio work on the electronic structure of lanthanide(III) ion calculated the crystal field splitting in an isostructural series of Ln(ODA)3 but without any experimental validation, and excluding neodymium(III) from the series. 67 Here, we resolve the electronic structure of the 18 lowest-lying energy states and the 2 emitting states in Nd(ODA)3 spectroscopically. We evaluate these results in light of ab initio calculations and find the calculations to be in good agreement with experimental results in terms of energy splitting for both the lower 4 IJ multiplets and the emitting states.…”

Section: Introductionmentioning

confidence: 99%

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Electronic Structure of a Neodymium(III) tris(oxydiacetate) Complex from Luminescence data and ab initio Calculations

Nielsen,

Grasser,

Mortensen

et al. 2024

Preprint

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Neodymium(III) is a NIR emissive and magnetic ion, which has found use in various high-technology applications. Yet, accurate predictions of the luminescent and magnetic properties of neodymium(III) based on the coordination environment remain to be done. Guideline exists, but to build structure-property relationships for this element, more data are needed. Herein, we present a high-symmetry starting point. The tris(oxydiacetate) complex of neodymium(III) was prepared and crystallised, and access to the experimentally determined structure allows us to quantify the symmetry of the compound and to perform calculations directly on the same structure that is investigated experimentally. The luminescent properties were determined and the electronic structure was computed using state-of-the-art ab initio methods. All electronic transitions in the range from 490 to 1400 nm were mapped experimentally. Using a Boltzmann population analysis, the combination of the excitation and emission spectra revealed the crystal field splitting of the 18 lowest energy Kramers levels that experimentally could be unambiguously resolved. This assignment was supported by ab initio calculations and the crystal field splitting was well reproduced. The electronic structure reported for the tris(oxydiacetate) complex is used to deduce the coordination structure in aqueous solution. Finally, the results are compared to empirical trends in the literature for the electronic structure of neodymium(III).

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Section: Molecular Structuresupporting

confidence: 63%

Section: Introductionmentioning

confidence: 99%

Electronic Structure of a Neodymium(III) tris(oxydiacetate) Complex from Luminescence data and ab initio Calculations

Nielsen,

Grasser,

Mortensen

et al. 2024

Preprint

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Electronic Structure of a Neodymium(III) Tris(oxidiacetate) Complex from Luminescence Data and Ab Initio Calculations

Nielsen,

Grasser,

Mortensen

et al. 2024

Inorg. Chem.

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Neodymium(III) is a near-infrared emissive and magnetic ion, which has found use in various high-technology applications. Yet, accurate predictions of the luminescent and magnetic properties of neodymium(III) based on the coordination environment remain to be done. Guidelines exist, but to build structure−property relationships for this element, more data are needed. Herein, we present a high-symmetry starting point. The tris(oxidiacetate) complex of neodymium(III) was prepared and crystallized, and access to the experimentally determined structure allowed us to quantify the symmetry of the compound and to perform calculations directly on the same structure that is investigated experimentally. The luminescent properties were determined and the electronic structure was computed using state-of-the-art ab initio methods. All electronic transitions in the range from 490 to 1400 nm were mapped experimentally. Using a Boltzmann population analysis, the combination of the excitation and emission spectra revealed the crystal field splitting of the 18 lowest-energy Kramers levels that experimentally could be unambiguously resolved. This assignment was supported by ab initio calculations, and the crystal field splitting was well reproduced. The electronic structure reported for the tris(oxidiacetate) complex was used to deduce the coordination structure in aqueous solution. Finally, the results are compared to empirical trends in the literature for the electronic structure of neodymium(III).

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In Search of Covalency Measure of Gd(III)-Ligand Interactions

Janicki,

Siczek,

Starynowicz

2024

J. Phys. Chem. Lett.

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Experimental electron density distribution of the [C(NH 2 ) 3 ] 3 [Gd(EDTA)F 2 ]•H 2 O crystal was determined. The derived experimental and theoretical (DFT) topological parameters such as ∇ 2 ρ c , ρ c , bond degree (BD), kinetics, and potential energy were used to study the nature of Gd−O, Gd−F, and Gd−N interactions. The natural charge of the Gd is 1.86; the natural configuration of the cation is [Xe]6s 0.13 4f 7.10 5d 0.83 , and the covalency of the Gd−L bond is mainly connected with the transfer of charge from the sp x ligand orbitals onto the 5d orbitals of the Gd cation. Simultaneously, the donation of charge onto the 6s and 4f orbitals occurs to a lesser extent. Moreover it was found that the donation of the ligand charges onto the Gd(III) is larger for compounds with a lower coordination number. The obtained topological parameters were analyzed in the context of the Gd(III) f−f transition properties, i.e., energy of the excited 2S+1 L J states, Judd−Ofelt intensity parameters, and luminescence lifetimes, of 18 Gd(III) compounds with various O, N, and F donor ligands (DOTA, EDTA, CDTA, DTPA, NTA, EGTA, ODA, F − , H 2 O, and CO 3 2−

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Ab Initio Investigation of the Na₃[Ln(ODA)₃]·2NaClO₄·6H₂O (Ln = Ce–Yb; ODA = Oxydiacetate) Series

Cited by 3 publications

References 70 publications

Electronic Structure of a Neodymium(III) tris(oxydiacetate) Complex from Luminescence data and ab initio Calculations

Electronic Structure of a Neodymium(III) tris(oxydiacetate) Complex from Luminescence data and ab initio Calculations

Electronic Structure of a Neodymium(III) Tris(oxidiacetate) Complex from Luminescence Data and Ab Initio Calculations

In Search of Covalency Measure of Gd(III)-Ligand Interactions

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