Luminescent dysprosium single-molecule magnets made from designed chiral BINOL-derived bisphosphate ligands

Mattei, Carlo Andrea; Montigaud, Vincent; Dorcet, Vincent; Riobé, François; Argouarch, Gilles; Maury, Olivier; Guennic, Boris Le; Cador, Olivier; Lalli, Claudia; Pointillart, Fabrice

doi:10.1039/d0qi01193b

Cited by 23 publications

(36 citation statements)

References 85 publications

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“…The X‐ray structure of [( R )‐1] n 51 and the dysprosium analogs of [( S , S , S )‐2] n and [( S , S , S )‐4] n 52 were previously determined on single crystal, and their purity phase was checked for both enantiomers by powder XRD. The quality of the single crystals of [( S , S , S )‐2] n , [( S )‐3] n , and [( S , S , S )‐4] n did not allow a satisfying refinement of the structures.…”

Section: Resultsmentioning

confidence: 99%

Circularly polarized luminescence of Eu(III) complexes with chiral 1,1′‐bi‐2‐naphtol‐derived bisphosphate ligands

et al. 2021

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The interest for lanthanide circularly polarized luminescence (CPL) has been quickly growing for 10 years. However, very few of these studies have involved correlation between the dissymmetry factor (g lum ) and the chemical modifications in a series of chiral ligands. Four polymeric compounds of Eu(III) were prepared by using a series of binaphtyl derivatives for which the size of the π system as well as the number of stereogenic elements (i.e., the binaphtyl moiety) are modulated. The resulting {[Eu(hfac) 3 ((S)/(R)-L x )]} n (x = 1 and 3) and {[Eu(hfac) 3 ((S,S,S)/(R,R,R)-L x )]} n (x = 2 and 4) have been characterized by powder X-ray diffraction by comparison with the X-ray structures on single crystal of the Dy(III) analogs. In solution, the structure of the complexes is deeply modified and becomes monomeric. The nature of the ligand induces change in the shape of the CPL spectra in CH 2 Cl 2 solution. Furthermore, a large jg lum j = 0.12 of the magnetic-dipole transition for the [Eu(hfac) 3 ((S,S,S)/ (R,R,R)-L 2 )] complex involving the ligand with three stereogenic elements and an extended π system has been measured. This report also shows CPL measurements in solid state for the series of {[Eu(hfac) 3 ((S)/(R)-L x )]} n (x = 1 and 3) and {[Eu(hfac) 3 ((S,S,S)/(R,R,R)-L x )]} n (x = 2 and 4) polymers.

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Section: Resultsmentioning

confidence: 99%

Circularly polarized luminescence of Eu(III) complexes with chiral 1,1′‐bi‐2‐naphtol‐derived bisphosphate ligands

et al. 2021

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“…The compounds 1 and 2 displayed a magnetic relaxation mainly through a pure Raman process (Figure 4, Figure 6 and Figure S9), which could be justified by the applied magnetic field (cancelling of the QTM), the moderate value of the field (the direct process is not the fastest magnetic relaxation process) and the low temperature range at which the relaxation times are extracted (below 10 K), leading to a negligible Orbach contribution. Recently, several Dy III -based SMMs displaying pure Raman magnetic relaxation under moderate applied field in the low temperature range have been reported [43][44][45][46][47][48][49]. For some of the reported example in Table 1, an Orbach process can be involved in the magnetic relaxation in the high temperature range, in which an out-of-phase contribution of the magnetic susceptibility was measured.…”

Section: Dynamic Magnetic Measurementsmentioning

confidence: 96%

Field-Induced Single-Molecule Magnets of Dysprosium Involving Quinone Derivatives

et al. 2021

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The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the two quinone-based derivatives 4,7-di-tert-butyl-2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)benzo[d][1,3]dithiole-5,6-dione (L1) and 7,8-dithiabicyclo[4.2.0]octa-1,5-diene-3,4-dione,2,5bis(1,1-dimethylethyl) (L2) led respectively to the complexes [Dy(hfac)3(H2O)(L1)] (1) and [Dy(hfac)3(H2O) (L2)]⋅(C6H14)(CH2Cl2) (2)⋅(C6H14)(CH2Cl2). X-ray structures on single crystal of 1 and 2⋅(C6H14)(CH2Cl2) revealed the coordination of the DyIII on the bischelating oxygenated quinone site and the formation of dimeric species through hydrogen bonds. Ac magnetic measurements highlighted field-induced single-molecule magnet behavior with magnetic relaxation through a Raman process.

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“…In such molecular objects, the chirality comes from a stereogenic center [24][25] helix [26] or axis [27]. In case of axial chirality, one of the most used ligands are the 2,2'-bis(diphenylphosphoryl)-1,1'-binaphthyl (BINAPO) and its bisphosphate analogues [28][29][30][31][32] because molecules bearing phosphine oxide groups are well known to efficiently coordinate Ln III ions [33].…”

Section: Introductionmentioning

confidence: 99%

Luminescent and Sublimable Binaphthyl-Based Field-Induced Lanthanide Single-Molecule Magnets

Pointillart¹,

Bouit²,

Riobé³

et al. 2022

Chem.Sq.

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The association of the [Ln(hfac)3(H2O)2] metallic building blocks with the new ligand [1,1’-binaphthalene]-8,8’-diylbis(diphenylphosphine oxide) (L) led to the formation of three mononuclear complexes of formula [Ln(hfac)3(L)] (LnIII = Eu (1), Dy (2) and Yb (3)). The mononuclear character of the compounds is due to the bidentate coordination mode adopted by L to link the metal. L allows the observation of the characteristic visible 5D0  7FJ (J = 0-4) EuIII- and near infrared 2F5/2  2F7/2 YbIII- emissions while 2 is only weakly emissive due to the mismatch between the energy positions of the triplet excited state of the ligand and DyIII emissive state. The magnetic data reveal a field-induced Single-Molecule Magnet (SMM) behavior for 2 and 3 with an efficient suppression of the Quantum Tunneling of the Magnetization (QTM). The slow magnetic relaxation occurs through a Raman process while the Orbach contribution is discarded as confirmed by the correlation with the MJ states energy splitting provided by the luminescence spectrum of 3.

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Luminescent dysprosium single-molecule magnets made from designed chiral BINOL-derived bisphosphate ligands

Abstract: The nature of the aromatic system and the number of chiral centers of the BINOL derived bisphosphate ligands influence both the chiroptical properties and single-molecule magnet behavior of a series of dysprosium-based chains.

Cited by 23 publications

References 85 publications

Circularly polarized luminescence of Eu(III) complexes with chiral 1,1′‐bi‐2‐naphtol‐derived bisphosphate ligands

Circularly polarized luminescence of Eu(III) complexes with chiral 1,1′‐bi‐2‐naphtol‐derived bisphosphate ligands

Field-Induced Single-Molecule Magnets of Dysprosium Involving Quinone Derivatives

Luminescent and Sublimable Binaphthyl-Based Field-Induced Lanthanide Single-Molecule Magnets

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