Divalent Thulium Triflate: A Structural and Spectroscopic Study

Xémard, Mathieu; Jaoul, Arnaud; Cordier, Marie; Molton, Florian; Cador, Olivier; Guennic, Boris Le; Duboc, Carole; Maury, Olivier; Clavaguéra, Carine; Nocton, Grégory

doi:10.1002/anie.201700576

Cited by 27 publications

(39 citation statements)

References 58 publications

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“…Divalent ions of these three metals have now been reported, mainly as cyclopentadienyl derivatives, and the majority involving thulium [35c, 56b, 68] . A few notable recent examples include a divalent thulium complex [Tm( μ ‐OTf) 2 (dme) 2 ] n ( 18 ) on which the first molecular Tm II luminescent measurements were reported [68a] . The luminescent measurements in corroboration with extensive EPR studies were used to unambiguously define the nature of the electronic ground state [68a] .…”

Section: Lanthanoid Complexes With Unusual Lanthanoid Oxidation Statesmentioning

confidence: 98%

“…A few notable recent examples include a divalent thulium complex [Tm( μ ‐OTf) 2 (dme) 2 ] n ( 18 ) on which the first molecular Tm II luminescent measurements were reported [68a] . The luminescent measurements in corroboration with extensive EPR studies were used to unambiguously define the nature of the electronic ground state [68a] . Soon after, Tm II in the crown ether complex [TmI 2 (18‐crown‐6)] ( 19 ) was found to display field induced slow relaxation of magnetization [35c] .…”

Section: Lanthanoid Complexes With Unusual Lanthanoid Oxidation Statesmentioning

confidence: 99%

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Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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The development of molecular materials with novel functionality offers promise for technological innovation. Switchable molecules that incorporate redox‐active components are enticing candidate compounds due to their potential for electronic manipulation. Lanthanoid metals are most prevalent in their trivalent state and usually redox‐activity in lanthanoid complexes is restricted to the ligand. The unique electronic and physical properties of lanthanoid ions have been exploited for various applications, including in magnetic and luminescent materials as well as in catalysis. Lanthanoid complexes are also promising for applications reliant on switchability, where the physical properties can be modulated by varying the oxidation state of a coordinated ligand. Lanthanoid‐based redox activity is also possible, encompassing both divalent and tetravalent metal oxidation states. Thus, utilization of redox‐active lanthanoid metals offers an attractive opportunity to further expand the capabilities of molecular materials. This review surveys both ligand and lanthanoid centered redox‐activity in pre‐existing molecular systems, including tuning of lanthanoid magnetic and photophysical properties by modulating the redox states of coordinated ligands. Ultimately the combination of redox‐activity at both ligands and metal centers in the same molecule can afford novel electronic structures and physical properties, including multiconfigurational electronic states and valence tautomerism. Further targeted exploration of these features is clearly warranted, both to enhance understanding of the underlying fundamental chemistry, and for the generation of a potentially important new class of molecular material.

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Section: Lanthanoid Complexes With Unusual Lanthanoid Oxidation Statesmentioning

confidence: 98%

Section: Lanthanoid Complexes With Unusual Lanthanoid Oxidation Statesmentioning

confidence: 99%

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Hay

Boskovic

2021

Chemistry A European J

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“…They showed that TPSS was one of the best density functionals, and that less accurate results were obtained when more Hartree–Fock exchange was included in the functional. Furthermore, lanthanide and actinide chemical properties have been extensively explored using DFT; for example, using the PBE0 density functional, or B3PW91 for mechanistic studies . Nonetheless, there is a lack of comparison between experimental data and computed data using different types of density functionals, for example, double hybrid functionals.…”

Section: Introductionmentioning

confidence: 99%

Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

2017

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The equilibrium between the radical phenanthroline complex Cp*2Sm(phen) and the coupling product (Cp*2Sm(phen))2 has been investigated based on quantum chemistry calculations. Topological analyses pointed out that the C−C bond created has a partial covalent character, explaining why both the monomeric and the dimeric forms exist in equilibrium. A large variety of density functionals have been tested to reproduce experimental thermodynamic data for this equilibrium. Finally, the PBE0‐D3 and M06‐2X functionals lead to a good evaluation of the energies and enable a correct description of the ligand to metal charge transfer, both in the 4f and 5d metal orbitals.

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“…[Cu(Psalen OMe )](SbF 6 ) exhibits a c value of about 0.00070(5) cm 3 mol À1 while [Cu(Psalen tBu )](SbF 6 ) has a c value of about 0.0001(1) cm 3 mol À1 .B oth values are low but positive which indicates at emperature independentp aramagnetic (TIP) [39] behavior albeit the c value is more than seven times higher in [Cu(Psalen OMe )](SbF 6 ) than in [Cu(Psalen tBu )](SbF 6 ).I n these cases, the purity of the sample was corrected for magnetic impurities, [40] and the nature of the sample containment was chosen according to previousr eports (see Supporting Information for details). [41] The observation of this TIP behavior over the large temperature range indicates that the triplet state is not populated-or to av ery smalle xtent-at room temperature and this is in favor of ar elative large gap (À2J) between the open-shell singlet andt he triplet states (above 1000 cm À1 ).…”

Section: Magnetic Studiesmentioning

confidence: 99%

Electronic Structures of Mono‐Oxidized Copper and Nickel Phosphasalen Complexes

Marín

Cheisson

Singh-Chauhan

et al. 2017

Chemistry A European J

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Non-innocent ligands render the determination of the electronic structure in metal complexes difficult. As such, a combination of experimental techniques and quantum chemistry are required to correctly elucidate them. This paper deals with the one-electron oxidation of copper(II) and nickel(II) complexes featuring a phosphasalen ligand (Psalen), which differs from salen analogues by the presence of iminophosphorane groups (P=N) instead of imines. Various experimental techniques (X-ray diffraction, cyclic voltammetry, NMR, EPR, and UV/Vis spectroscopies, and magnetic measurements) as well as quantum chemical calculations were used to define the electronic structure of the oxidized complexes. These can be modified by a small change in the ligand structure, that is, the replacement of a tert-butyl group by a methoxy on the phenoxide ring. The different techniques have allowed quantifying the amount of spin density located on the metal center and on the Psalen ligands. All complexes were found to possess a multi-configurational ground state, in which the ratio of the +II versus +III oxidation state of the metal center, and therefore the phenolate versus phenoxyl radical ligand character, varies upon the substituents. The tert-butyl group favors a strong localization on the metal center whereas with the methoxy group the metallic configurations decrease and the ligand configurations increase. The importance of the geometrical considerations compared with the electronic substituent effect is highlighted by the differences observed between the solid-state (EPR, magnetic measurements) and solution characterizations (EPR and NMR data).

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Divalent Thulium Triflate: A Structural and Spectroscopic Study

Cited by 27 publications

References 58 publications

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Lanthanoid Complexes as Molecular Materials: The Redox Approach

Assessment of Density Functionals for Computing Thermodynamic Properties of Lanthanide Complexes

Electronic Structures of Mono‐Oxidized Copper and Nickel Phosphasalen Complexes

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