Hohe Block‐Temperatur der Magnetisierung und herausragende Koerzitivfeldstärke im Azafulleren Tb<sub>2</sub>@C<sub>79</sub>N mit einer Einelektronen‐Terbium‐Terbium‐Bindung

Velkos, Georgios; Krylov, Denis; Kirkpatrick, Kyle; Spree, Lukas; Dubrovin, Vasilii; Büchner, B.; Avdoshenko, Stanislav M.; Bezmelnitsyn, Valeriy; Davis, Sean; Faust, Paul; Duchamp, James C.; Dorn, Harry C.; Popov, Alexey A.

doi:10.1002/ange.201900943

Cited by 13 publications

(6 citation statements)

References 57 publications

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“…Indeed, the experimental evidence of the metal–metal bond in pristine Lu 2 @C 82–86 (Y 2 @C 82 ) isomers presents a TETC bond between the two Lu (Y) ions and it is proposed that the isomers are thermodynamically favorable by forming the two‐electron occupied Lu−Lu (Y−Y) bond . Meanwhile, the one‐electron‐two‐center (OETC) metal–metal bond, which possesses a radical bridge between the two metals, has also been intensively studied in the encapsulated lanthanide dimers of La, Y, Gd, Tb, Dy, Ho, and Er . Commonly, the systems are all stabilized by the derivatization of the pristine EMFs or by the substitution of a cage carbon with a nitrogen instead; however, the study of OETC metal–metal bonds in pristine EMFs are rarely available thus far.…”

Section: Introductionmentioning

confidence: 99%

Crystallographic and Theoretical Investigations of Er₂@C_2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature

Shen

Yang

et al. 2019

Chemistry A European J

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Successful isolation and characterization of a series of Er‐based dimetallofullerenes present valuable insights into the realm of metal–metal bonding. These species are crystallographically identified as Er2@Cs(6)‐C82, Er2@C3v(8)‐C82, Er2@C1(12)‐C84, and Er2@C2v(9)‐C86, in which the structure of the C1(12)‐C84 cage is unambiguously characterized for the first time by single‐crystal X‐ray diffraction. Interestingly, natural bond orbital analysis demonstrates that the two Er atoms in Er2@Cs(6)‐C82, Er2@C3v(8)‐C82, and Er2@C2v(9)‐C86 form a two‐electron‐two‐center Er−Er bond. However, for Er2@C1(12)‐C84, with the longest Er⋅⋅⋅Er distance, a one‐electron‐two‐center Er−Er bond may exist. Thus, the difference in the Er⋅⋅⋅Er separation indicates distinct metal bonding natures, suggesting a distance‐dependent bonding behavior for the internal dimetallic cluster. Additionally, electrochemical studies suggest that Er2@C82–86 are good electron donors instead of electron acceptors. Hence, this finding initiates a connection between metal–metal bonding chemistry and fullerene chemistry.

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Section: Introductionmentioning

confidence: 99%

Crystallographic and Theoretical Investigations of Er₂@C_2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature

Shen

Yang

et al. 2019

Chemistry A European J

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“…This observation conforms with the understanding of the previously reported SEMBcontaining homonuclear di-EMFs M 2 @C 79 N and M 2 @ C 80 (C 7 H 7 ) (M = Sc, Y, La, Gd, Tb, Dy, Ho, Er). [5][6][7][8][9][10]12,13 However, a clear difference is present in heteronuclear LaTi@ I h (7)-C 80 , where the SOMO and the spin density distribution are concentrated closer to Ti (see Figure 4a,b). This indicates that the unpaired electron comes from Ti with a 3d 1 electronic configuration and thus a formal trivalent state for both metals.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

Steering Single-Electron Metal–Metal Bonds and Hyperfine Coupling between a Transition Metal-Lanthanide Heteronuclear Bimetal Confined in Carbon Cages

Xiang,

Hu,

Xin

et al. 2023

J. Am. Chem. Soc.

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Metal complexes bearing single-electron metal− metal bonds (SEMBs) exhibit unusual electronic structures evoking strong magnetic coupling, and such bonds can be stabilized in the form of dimetallofullerenes (di-EMFs) in which two metals are confined in a carbon cage. Up to now, only a few di-EMFs containing SEMBs are reported, which are all based on a high-symmetry icosahedral (I h ) C 80 cage embedding homonuclear rare-earth bimetals, and a chemical modification of the I h -C 80 cage is required to stabilize the SEMB. Herein, by introducing 3d-block transition metal titanium (Ti) along with 4f-block lanthanum (La) into the carbon cage, we synthesized the first crystallographically characterized SEMB-containing 3d−4f heteronuclear di-EMFs based on pristine fullerene cages. Four novel La−Ti heteronuclear di-EMFs were isolated, namely, LaTi@D 3h (5)-C 78 , LaTi@ I h (7)-C 80 , LaTi@D 5h (6)-C 80 , and LaTi@C 2v (9)-C 82 , and their molecular structures were unambiguously determined by single-crystal X-ray diffraction. Upon increasing the cage size from C 78 to C 82 , the La−Ti distance decreases from 4.31 to 3.97 Å, affording finetuning of the metal−metal bonding and hyperfine coupling, as evidenced by an electron spin resonance (ESR) spectroscopic study. Density functional theory (DFT) calculations confirm the existence of SEMB in all four LaTi@C 2n di-EMFs, and the accumulation of electron density between La and Ti atoms shifts gradually from the proximity of the Ti atom inside C 78 to the center of the LaTi bimetal inside C 82 due to the decrease of the La−Ti distance. The electronic properties of LaTi@C 2n heteronuclear dimetallofullerenes differ apparently from their homonuclear La 2 @C 2n counterparts, revealing the peculiarity of heteronuclear dimetallofullerenes with the involvement of 3d-block transition metal Ti.

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“…Many Ln SMMs with two metal ions are reported. [128][129][130][131] For example, J.F. Long et al linked two Ln ions by N 2 3À radicals to construct a series of binuclear SMMs-{Ln 2 (μ: η 2 : η 2 -N 2 )} (Ln = Tb (13), Ho (14), Er (15), Figure 9a).…”

Section: Dinuclear Ln Smmsmentioning

confidence: 99%

“…Magnetic interactions occur when the distance of the two atoms is smaller than 10 Å, and on the contrary it can be ignored. Many Ln SMMs with two metal ions are reported [128–131] . For example, J.F.…”

Section: Recent Advances Of Ln Smmsmentioning

confidence: 99%

Lanthanide Single‐molecule Magnets: Synthetic Strategy, Structures, Properties and Recent Advances

Wang

Sun

Zheng

et al. 2023

Chemistry An Asian Journal

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Single-molecule magnets (SMMs) show wide potential applications in the field of ultrahigh-density storage materials, quantum computing, spintronics, and so on. Lanthanide (Ln) SMMs, as an important category of SMMs, open up a promising prospect due to their large magnetic moments and huge magnetic anisotropy. However, the construction of high performance for Ln SMMs remains an enormous challenge. Although remarkable advances are focused on the topic of Ln SMMs, the research on Ln SMMs with different nuclear numbers is still deficient. Therefore, this review summarizes the design strategies for the con-struction of Ln SMMs, as well as the metal skeleton types. Furthermore, we collect reported Ln SMMs with mononuclearity, dinuclearity, and multinuclearity (three or more Ln spin centers) and the SMM properties including energy barrier (U eff ) and pre-exponential factor (τ 0 ) are described. Finally, Ln SMMs with low-nuclearity SMMs, especially for single-ion magnets (SIMs), are highlighted to understand the correlations between structures and magnetic behavior of the detail SMM properties are described. We expect the review can shed light on the future developments of highperformance Ln SMMs.

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Hohe Block‐Temperatur der Magnetisierung und herausragende Koerzitivfeldstärke im Azafulleren Tb₂@C₇₉N mit einer Einelektronen‐Terbium‐Terbium‐Bindung

Cited by 13 publications

References 57 publications

Crystallographic and Theoretical Investigations of Er₂@C_2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature

Crystallographic and Theoretical Investigations of Er₂@C_2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature

Steering Single-Electron Metal–Metal Bonds and Hyperfine Coupling between a Transition Metal-Lanthanide Heteronuclear Bimetal Confined in Carbon Cages

Lanthanide Single‐molecule Magnets: Synthetic Strategy, Structures, Properties and Recent Advances

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Hohe Block‐Temperatur der Magnetisierung und herausragende Koerzitivfeldstärke im Azafulleren Tb2@C79N mit einer Einelektronen‐Terbium‐Terbium‐Bindung

Cited by 13 publications

References 57 publications

Crystallographic and Theoretical Investigations of Er2@C2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature

Crystallographic and Theoretical Investigations of Er2@C2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature

Steering Single-Electron Metal–Metal Bonds and Hyperfine Coupling between a Transition Metal-Lanthanide Heteronuclear Bimetal Confined in Carbon Cages

Lanthanide Single‐molecule Magnets: Synthetic Strategy, Structures, Properties and Recent Advances

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Hohe Block‐Temperatur der Magnetisierung und herausragende Koerzitivfeldstärke im Azafulleren Tb₂@C₇₉N mit einer Einelektronen‐Terbium‐Terbium‐Bindung

Crystallographic and Theoretical Investigations of Er₂@C_2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature

Crystallographic and Theoretical Investigations of Er₂@C_2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature