Modulation of Homochiral Dy<sup>III</sup> Complexes: Single‐Molecule Magnets with Ferroelectric Properties

Li, Xi-Li; Chen, Chun-Lai; Gao, Yu-Liang; Liu, Cai‐Ming; Xie, Feng; Gui, Yanghai; Fang, Shaoming

doi:10.1002/chem.201201190

Cited by 96 publications

(41 citation statements)

References 87 publications

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“…Moreover, the magnetic interactions (exchange and dipolar) between the Dy III ions transmitted by the bridging ligand can contribute to quench QTM and to observe the real energy barrier ( U ) for magnetization reversal. It is worth mentioning that the examples of coordination compounds where SMM and chirality coexist are scarce (Domingo et al, 2003 ; Singh et al, 2009 ; Inglis et al, 2011 ; Novitchi et al, 2011 , 2012 ; Zhu et al, 2011 , 2014 ; Li et al, 2012 ; Wang et al, 2014 ; Ou-Yang et al, 2016 ; Wada et al, 2016 ; Escuer et al, 2017 ; Fernandez-Garcia et al, 2017 ; Lippert et al, 2017 ; Liu M.-J. et al, 2017 ; Peng et al, 2017 ; Wen et al, 2018 ).…”

Section: Introductionmentioning

confidence: 99%

A Chiral Bipyrimidine-Bridged Dy2 SMM: A Comparative Experimental and Theoretical Study of the Correlation Between the Distortion of the DyO6N2 Coordination Sphere and the Anisotropy Barrier

et al. 2018

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Chiral bipyrimidine-bridged dinuclear LnIII complexes of general formula [(μ-bipym){((+)-tfacam)3Ln}2] and [(μ-bipym){((-)-tfacam)3Ln}2], have been prepared from the assembly of Ln(AcO)3·nH2O (LnIII = Dy, Gd), (+)/(−)-3-(trifluoroacetyl)camphor enantiopure ligands ((+)/(-)-Htfacam) and bipyrimidine (bipym). The structure and chirality of these complexes have been supported by single-crystal X-Ray diffraction and circular dichroism. The study of the magnetic properties of the GdIII complexes revealed a very weak antiferromagnetic interaction between the GdIII ions through the bipyrimidine bridging ligand. Ab initio CASSCF calculations indicated that the ground Kramers doublet (KD) of both DyIII centers is almost purely axial with the anisotropy axis located close to the two tfacam−ligands at opposite sides of each DyIIIatom, which create an axial crystal field. In keeping with this, ac dynamic measurements indicated slow relaxation of the magnetization at zero field with Ueff = 55.1 K, a pre-exponential factor of τo = 2.17·10−6 s and τQTM = 8 μs. When an optimal dc field of 0.1 T is applied, QTM is quenched and Ueff increases to 75.9 K with τo = 6.16 × 10−7 s. The DyN2O8 coordination spheres and SMM properties of [(μ-bipym){((+)-tfacam)3Ln}2] and their achiral [(Dy(β-diketonate)3)2(μ-bpym)]analogous have been compared and a magneto-structural correlation has been established, which has been supported by theoretical calculations. In contrast to the GdIII compounds, the magnetic exchange interaction between the DyIII ions has been calculated to be very weak and, generally, ferromagnetic in nature. Relaxation mechanisms for [(μ-bipym){((+)-tfacam)3Ln}2] and previously reported analogous have been proposed from ab initio calculations. As the magnetic exchange interaction found to be very weak, the observed magnetization blockade in these systems are primarily dictated by the single ion anisotropy of DyIII ions.

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Section: Introductionmentioning

confidence: 99%

A Chiral Bipyrimidine-Bridged Dy2 SMM: A Comparative Experimental and Theoretical Study of the Correlation Between the Distortion of the DyO6N2 Coordination Sphere and the Anisotropy Barrier

et al. 2018

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“…Enantiopure SCO compounds may offer new physical properties, for example, magnetochiral dichroism . Thus, to achieve this goal one method of designing chiral SCO compounds is to construct coordination complexes from paramagnetic centers with a d 4 to d 7 electronic configuration and suitable chiral ligands . We therefore employed pinene groups as chiral sources, as they were proven to be effective for deriving chiral functional materials .…”

Section: Introductionmentioning

confidence: 99%

Three Properties in One Coordination Complex: Chirality, Spin Crossover, and Dielectric Switching

Shi

et al. 2017

Eur J Inorg Chem

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In the search for multifunctional molecular materials, we designed an enantiopure pair of FeII complexes with chiral, chelating (R)/(S)‐4,5‐pinenepyridyl‐2‐pyrazine ligands exhibiting three inherent physical properties: chirality, spin crossover, and dielectric switching. The geometrical change resulted in coupling of the spin‐crossover transition at 187 K to dielectric switching. Both compounds were found to display light‐induced spin crossover that was thermally unstable above ca. 40 K. The coupling of two hysteretic properties, electric and magnetic, renders these compounds as potential switching devices.

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“…In a general manner, the addition of one or more physical properties to the SMM behavior paves the way to the design of multi-properties SMM as well as the study of a possible synergy between the different properties. Moreover, when chirality is added to the (luminescent) SMM behavior [21][22][23][24][25][26][27][28], chiral SMM [29], ferroelectric SMM [30] as well as chiral luminescent SMM [31][32][33][34][35][36] and magneto-chiral SMM [37,38] can be obtained. To these three properties, the introduction of redox-active ligands is of interest because it could permit to switch both optical and magnetic properties depending on the oxidation state of the ligand [39][40][41][42][43][44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand

et al. 2021

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The reactions between the bis(1,10-phenantro[5,6-b])tetrathiafulvalene triad (L) and the metallo-precursors Yb(hfac)3(H2O)2 (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonato anion) and Dy(facam)3 (facam− = 3-trifluoro-acetyl-(+)-camphorato anion) lead to the formation of two dinuclear complexes of formula [Yb2(hfac)6(L)]·2(C7H16) ((1)·2(C7H16)) and [Dy2((+)facam)6(L)]·2(C6H14) ((2)·2(C6H14)). The X-ray structures reveal that the L triad bridges two terminal Yb(hfac)3 or Dy(facam)3 units. (1)·2(C7H16) behaved as a near infrared YbIII centered emitter and a field-induced Single-Molecule Magnet (SMM) while (2)·2(C6H14) displayed SMM behavior in both zero- and in-dc field. The magnetization mainly relaxes through a Raman process for both complexes under an optimal applied magnetic field.

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Modulation of Homochiral Dy^III Complexes: Single‐Molecule Magnets with Ferroelectric Properties

Cited by 96 publications

References 87 publications

A Chiral Bipyrimidine-Bridged Dy2 SMM: A Comparative Experimental and Theoretical Study of the Correlation Between the Distortion of the DyO6N2 Coordination Sphere and the Anisotropy Barrier

A Chiral Bipyrimidine-Bridged Dy2 SMM: A Comparative Experimental and Theoretical Study of the Correlation Between the Distortion of the DyO6N2 Coordination Sphere and the Anisotropy Barrier

Three Properties in One Coordination Complex: Chirality, Spin Crossover, and Dielectric Switching

Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand

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Modulation of Homochiral DyIII Complexes: Single‐Molecule Magnets with Ferroelectric Properties

Cited by 96 publications

References 87 publications

A Chiral Bipyrimidine-Bridged Dy2 SMM: A Comparative Experimental and Theoretical Study of the Correlation Between the Distortion of the DyO6N2 Coordination Sphere and the Anisotropy Barrier

A Chiral Bipyrimidine-Bridged Dy2 SMM: A Comparative Experimental and Theoretical Study of the Correlation Between the Distortion of the DyO6N2 Coordination Sphere and the Anisotropy Barrier

Three Properties in One Coordination Complex: Chirality, Spin Crossover, and Dielectric Switching

Chiral or Luminescent Lanthanide Single-Molecule Magnets Involving Bridging Redox Active Triad Ligand

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Modulation of Homochiral Dy^III Complexes: Single‐Molecule Magnets with Ferroelectric Properties