Ab initio calculations with effective core potentials on trivalent lanthanide-terpyridine complexes

Rabbe, C.; Mikhalko, V. K.; Dognon, Jean-Pierre

doi:10.1007/s002140000119

Cited by 18 publications

(6 citation statements)

References 7 publications

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“…The calculated M–N distances (Table 2) show that, in the gas phase, this higher affinity for Co II is also present: bond lengths are always longer for Cd II – than for Co II –pyridine systems, these differences being more marked for the less stable M II –py complexes (0.387 Å longer in Cd II –py than in Co II –py). It is noteworthy that the difference in M–N in bond lengths calculated with DFT in Cd II – and Co II –terpy complexes (0.334 Å) is slightly higher than that of the M–N ex bond (0.331 Å): this is in agreement with previous studies which found that small cations are able to better interact with the central nitrogen, due to the steric constraint of this rigid ligand 49…”

Section: Discussionsupporting

confidence: 91%

Affinity of Polypyridines Towards Cd^II and Co^II Ions: a Thermodynamic and DFT Study

et al. 2006

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CdII and CoII complex formation with pyridine (py), 2,2′‐bipyridine (bipy), 2,2′6′,2″‐terpyridine (terpy), 2‐(aminomethyl)pyridine (amp), and bis[(2‐pyridyl)methyl]amine (dpma) was studied at 298 K in the aprotic solvent dimethyl sulfoxide (DMSO) and in an ionic medium set to 0.1 mol dm–3 with Et4NClO4 in anaerobic conditions. Potentiometric, UV/Vis spectrophotometric, and calorimetric measurements were carried out to obtain the thermodynamic parameters of the systems investigated. Enthalpy‐stabilized mononuclear MLj complexes are formed, whereas entropy changes counteract complex formation. These results are discussed in terms of different basicities, steric requirements, and solvation, of both the ligands and the resulting complexes. Density functional theory (DFT) calculations were carried out in order to obtain structural information and binding energies in vacuo. The DFT results are correlated with the solution studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Discussionsupporting

confidence: 91%

Affinity of Polypyridines Towards Cd^II and Co^II Ions: a Thermodynamic and DFT Study

et al. 2006

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“…The importance of relativistic effects in lanthanide complexes was examined by comparing the Ln-N bond distances in [Ln(tpy)] 3+ complexes calculated at the HF level with the large-core nonrelativistic [55] and quasirelativistic [47] pseudopotentials of Dolg et al The use of quasirelativistic pseudopotentials induced an increasing bond length contraction from La to Lu along the lanthanide series, as Lu exhibits larger relativistic effects than La [56].…”

Section: An Overview Of the Computational Methods For Treatment Of Lnmentioning

confidence: 99%

Applications of Density Functional Theory (DFT) to Investigate the Structural, Spectroscopic and Magnetic Properties of Lanthanide(III) Complexes

Platas‐Iglesias¹,

Roca-Sabio²,

Regueiro‐Figueroa³

et al. 2011

CIC

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Density functional theory (DFT) has become a general tool to investigate the structure and properties of complicated inorganic molecules, such as lanthanide(III) coordination compounds, due to the high accuracy that can be achieved at relatively low computational cost. Herein, we present an overview of different successful applications of DFT to investigate the structure, dynamics, vibrational spectra, NMR chemical shifts, hyperfine interactions, excited states, and magnetic properties of lanthanide(III) complexes. We devote particular attention to our own work on the conformational analysis of LnIII-polyaminocarboxylate complexes. Besides, a short discussion on the different approaches used to investigate lanthanide(III) complexes, i. e. all-electron relativistic calculations and the use of relativistic effective core potentials (RECPs), is also presented. The issue of whether the 4f electrons of the lanthanides are involved in chemical bonding or not is also shortly discussed.

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“…Additionally, the [51]. It is found that the calculated bond lengths are commonly longer than those measured in solid crystals, which is probably caused by the packing effects and the outer-sphere counterions in the complex crystals [37,58,59]. The Am-N bond lengths are comparable to those of Eu-N and the natural charges of Am(III) are mildly higher than those of Eu(III) in all the 1 : 2 complexes.…”

Section: Geometry and Nbo Analysismentioning

confidence: 66%

Selective separation of Am(III) from Eu(III) by 2,9-Bis(dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthrolines: a relativistic quantum chemistry study

et al. 2014

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The complexation properties of Am(III) and Eu(III) with a serial of novel -heterocyclic tetradentate ligands, 2,9-bis(dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthrolines (BTPhens), have been calculated by density functional theory (DFT) coupled with relativistic smallcore pseudopotential. It is found that the nitrogen atoms in triazine rings favor metal cations more than those in phenanthroline skeleton. The Am-N bond lengths are comparable to or even shorter than those of Eu-N bonds based on the larger radii of Am(III) than Eu(III). The effect of alkyl substituents on the complex structures is limited but they can adjust the complexation reaction and extraction kinetics. Additionally, the solvent effect can decrease the probability of the complexation reactions greatly and the solvation energies of Am(III) and Eu(III) might be the primary driving force in the complexation selectivity. The complexation reactions for forming ML(NO 3 ) 3 and [ML 2 (NO 3 )] 2+ complexes are believed to dominate the selective extraction separation of Am(III) from Eu(III) in nitric acid media, which agrees well with the experimental results. The comparisons of BTPhens with BTBPs in dipoles and electronic structures confirm that the BTPhens exhibit more favourable extraction kinetics and selectivity for minor actinides.

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Ab initio calculations with effective core potentials on trivalent lanthanide-terpyridine complexes

Cited by 18 publications

References 7 publications

Affinity of Polypyridines Towards Cd^II and Co^II Ions: a Thermodynamic and DFT Study

Affinity of Polypyridines Towards Cd^II and Co^II Ions: a Thermodynamic and DFT Study

Applications of Density Functional Theory (DFT) to Investigate the Structural, Spectroscopic and Magnetic Properties of Lanthanide(III) Complexes

Selective separation of Am(III) from Eu(III) by 2,9-Bis(dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthrolines: a relativistic quantum chemistry study

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Ab initio calculations with effective core potentials on trivalent lanthanide-terpyridine complexes

Cited by 18 publications

References 7 publications

Affinity of Polypyridines Towards CdII and CoII Ions: a Thermodynamic and DFT Study

Affinity of Polypyridines Towards CdII and CoII Ions: a Thermodynamic and DFT Study

Applications of Density Functional Theory (DFT) to Investigate the Structural, Spectroscopic and Magnetic Properties of Lanthanide(III) Complexes

Selective separation of Am(III) from Eu(III) by 2,9-Bis(dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthrolines: a relativistic quantum chemistry study

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Affinity of Polypyridines Towards Cd^II and Co^II Ions: a Thermodynamic and DFT Study

Affinity of Polypyridines Towards Cd^II and Co^II Ions: a Thermodynamic and DFT Study