Reversible Pressure-Magnetic Modulation in a Tetrathiafulvalene-Based Dyad Piezochromic Dysprosium Single-Molecule Magnet.

The extreme sensitivity of trivalent lanthanide ions to crystal field variations led to the emergence of single-molecule magnetic switching under various stimuli. The use of pressure as an external stimulus instead of classic light irradiation, oxidation or any chemical reactions allows a fine tuning of the magnetic modulation. Here the well-known pure isotopically enriched [162 Dy(tta)3 (L)]⋅C6 H14 (162 Dy) Single-Molecule Magnet (SMM) (tta- =2-2-thenoyltrifluoroacetonate and L=4,5-bis(propylthio)-tetrathiafulvalene-2-(2-pyridyl)benzimidazole-methyl-2-pyridine) was experimentally investigated by single-crystal diffraction and squid magnetometry under high applied pressures. Both reversible piezochromic properties and pressure modulation of the slow magnetic relaxation behavior were demonstrated and supported by ab initio calculations. The magnetic study of the diluted sample [162 Dy0.05 Y0.95 (tta)3 (L)]⋅C6 H14 (162 Dy@Y) indicated that variations in the electronic structure have mainly intermolecular origin with weak intramolecular contribution. Quantitative magnetic interpretation concludes to a deterioration of the Orbach process for the benefit of both Raman and QTM mechanisms under applied pressure.

Multifunctional Helicene-Based Ytterbium Coordination Polymer Displaying Circularly Polarized Luminescence, Slow Magnetic Relaxation and Room Temperature Magneto-Chiral Dichroism.

The combination of physical properties sensitive to molecular chirality in a single system allows the observation of fascinating phenomena such as magneto-chiral dichroism (MChD) and circularly polarized luminescence (CPL) having potential applications for optical data readout and display technology. Homochiral monodimensional coordination polymers of YbIII were designed from a 2,15-bis-ethynyl-hexahelicenic scaffold decorated with two terminal 4-pyridyl units. Thanks to the coordination of the chiral organic chromophore to Yb(hfac)3 units (hfac- =1,1,1,5,5,5-hexafluoroacetylaconate), efficient NIR-CPL activity is observed. Moreover, the specific crystal field around the YbIII induces a strong magnetic anisotropy which leads to a single-molecule magnet (SMM) behaviour and a remarkable room temperature MChD. The MChD-structural correlation is supported by computational investigations.

Bulky anion effect on the architecture of chiral dysprosium single-molecule magnets.

The interest for chiral tris(ß-diketonato)lanthanide complexes in coordination chemistry is huge due to its Lewis acid character, optical activity, and the control of the final compound architecture. The reaction of equimolar quantities of [Dy((-)/(+)hfc)3 (H2 O)] (hfc- = 3-(heptafluoropropylhydroxymethylene)-(+/-)-camphorate) and L led to the formation of a pair of enantiomers for dinuclear complexes [Dy((-)/(+)hfc)3 (L)]2 ⋅C7 H16 ([(-)/(+)1]⋅C7 H16 ) (L = 4'-(4'''-pyridyl-N-oxide)-1,2':6'1''-bis-(pyrazolyl)pyridine]). Starting from the previous experimental protocol with the addition of bulky BArF anions, a partial dissociation of the chiral [Dy((-)/(+)hfc)3 (H2 O)] was observed leading to the isolation of a mono-dimensional cationic chiral polymer {[Dy((-)/(+)hfc)2 (L)][BarF]}n ⋅nCH3 NO2 ([(-)/(+)2]n ⋅nCH3 NO2 ). Natural circular dichroism (NCD) highlighted an exciton CD couplet for [(-)/(+)2]n but not for (-)/(+)1. The latter behaves as a single-molecule magnet (SMM) with a blocking temperature up to 4 K, whereas [(-)/(+)2]n is a 1D assembly of field-induced SMMs with a magnetic relaxation occurring through a Raman process only.

Modulation of the magnetic and photophysical properties in 3d-4f and 4f-4f' heterobimetallic complexes involving a tetrathiafulvalene-based ligand.

The reaction between the 2-(1-(2,6-di(pyrazol-1-yl)-4-methylpyridyl)-4,5-(4,5-bis(propylthio)-tetrathiafulvalenyl)-1H-benzimidazol-2-yl)-pyridine ligand (L), 1 equivalent of Ln(hfac)3·2H2O/Dy(tta)3·2H2O (hfac- = 1,1,1,5,5,5-hexafluoroacetylacetonate, tta- = 2-thenoyltrifluoroacetonate) and M(hfac)2·2H2O leads to the formation of heteroleptic 3d-4f dinuclear complexes of formula [MLn(hfac)5(L)]n (M(II) = Cd, Zn, Co, Mn, Ni and Ln(III) = Dy, Yb, Nd) and [ZnDy(tta)2(hfac)3(L)]·(CH2Cl2). Their X-ray structures reveal that the two coordination sites are occupied by one Ln(III) ion and one M(II) transition metal respectively. The M(II) ions are coordinated to the benzoimidazolylpyridine (bzip) moiety in a N2O4 coordination sphere, while the Ln(III) ions are coordinated to the 2,6-di(pyrazol-1-yl)-4-pyridine (dpp) moiety in a N3O6 surrounding. When Dy(III) ion is used a field-induced Single-Molecule Magnet (SMM) behavior is detected with a magnetic relaxation time slightly dependent to the nature of the vicinal divalent transition metal. On the other hand, when the Yb(III) is used, intense, moderated or quenched 2F5/2 → 2F7/2 NIR luminescence is observed when the Yb(III) ion is respectively associated with the Zn(II), Mn(II) and Ni(II)/Co(II) ion. The emission intensity can be modulated in function of the metal-to-ligand charge transfer and d-d transition intensities. The replacement of the divalent transition metal by a trivalent lanthanide leads to the formation of heteroleptic 4f-4f' dinuclear complexes of formula [Ln2-xLn'x(hfac)6(L)]·a(CH2Cl2)·b(C6H14) and [Dy1.11Nd0.89(tta)3(hfac)3(L)]. The coordination selectivity is based on the radius. Among the 4f-4f' series, the Dy(III) derivatives displayed such ion in N2O6 eight-coordinated sphere allowing the observation of SMM behavior. The three compounds [Dy1.21Nd0.79(hfac)6(L)]·2(CH2Cl2)·(C6H14), [Yb1.04Nd0.96(hfac)6(L)] and [YbPr(hfac)6(L)] displayed respectively Nd(III), modarated Yb(III) and intense Yb(III) NIR emissions.

Helicene-Based Ligands Enable Strong Magneto-Chiral Dichroism in a Chiral Ytterbium Complex.

Here we report the first experimental observation of magneto-chiral dichroism (MChD) detected through light absorption in an enantiopure lanthanide complex. The P and M enantiomers of [YbIII((X)-L)(hfac)3] (X = P, M; L = 3-(2-pyridyl)-4-aza[6]-helicene; hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate), where the chirality is held by the helicene-based ligand, were studied in the near-infrared spectral window. When irradiated with unpolarized light in a magnetic field, these chiral complexes exhibit a strong MChD signal (gMChD ca. 0.12 T-1) associated with the 2F5/2 ← 2F7/2 electronic transition of YbIII. The low temperature absorption and MChD spectra reveal a fine structure associated with crystal field splitting and vibronic coupling. The temperature dependence of the main dichroic signal detected up to 150 K allowed, for the first time, the disentanglement of the two main microscopic contributions to the dichroic signal predicted by the MChD theory. These findings pave the way toward probing MChD in chiral lanthanide-based single-molecule magnets.

Ytterbium-Centered Isotopic Enrichment Leading to a Zero-Field Single-Molecule Magnet.

An unprecedented combination of isotopic enrichment and magnetic dilution approaches for a prolate ytterbium(III)-based complex was performed. It results in the appearance of the first observations of a nuclear spin effect on both quantum tunneling of magnetization and slow magnetic relaxation for an ytterbium complex under a zero applied field.