A trinuclear metallasilsesquioxane of uranium(<scp>iii</scp>)

Tricoire, Maxime; Jori, Nadir; Fadaei Tirani, Farzaneh; Scopelliti, Rosario; Z̆ivković, Ivica; Natrajan, Louise S.; Mazzanti, Marinella

doi:10.1039/d3cc05390c

Cited by 3 publications

(1 citation statement)

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“…Significantly, complexes exhibiting unambiguous magnetic exchange between uranium(III) centers are exceedingly rare. To the best of our knowledge, other known examples include the recently reported triuranium cluster U 3 ( i Bu POSS) 3 ( i Bu POSSH 3 = ( i Bu) 7 Si 7 O 9 (OH) 3 ), [Cs 2 {U(OSi(O t Bu) 3 ) 3 } 2 (μ-O)], [U(OSi(O t Bu) 3 ) 2 (μ-OSi(O t Bu) 3 )] 2 , [U(N**)] 2 (μ–I) 2 , [K 3 {[U(OSi(O t Bu) 3 ) 3 ] 2 (μ-N)}], and (μ-toluene)U 2 (N[ t Bu]Ar) 4 (Ar = 3,5-C 6 H 3 Me 2 ) . Similar to 1-X , these compounds exhibit covalent uranium–bridging ligand bonding in tandem with antiferromagnetic exchange, with maxima in χ M versus T at approximately 6, 10, 16, 17, 23, and 125 K, respectively.…”

Section: Resultsmentioning

confidence: 99%

Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp^iPr5)₃U₃X₆ (X = Cl, Br, I) Clusters

Lussier,

Ito,

McClain

et al. 2024

J. Am. Chem. Soc.

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The actinide elements are attractive alternatives to transition metals or lanthanides for the design of exchange-coupled multinuclear single-molecule magnets. However, the synthesis of such compounds is challenging, as is unraveling any contributions from exchange coupling to the overall magnetism. To date, only a few actinide compounds have been shown to exhibit exchange coupling and single-molecule magnetism. Here, we report triangular uranium(III) clusters of the type (Cp iPr5 ) 3 U 3 X (1-X; X = Cl, Br, I; Cp iPr5 = pentaisopropylcyclopentadienyl), which are synthesized via reaction of the aryloxide-bridged precursor (Cp iPr5 ) 2 U 2 (OPh tBu ) 4 with excess Me 3 SiX. Spectroscopic analysis suggests the presence of covalency in the uranium−halide interactions arising from 5f orbital participation in bonding. The dc magnetic susceptibility data reveal the presence of antiferromagnetic exchange coupling between the uranium(III) centers in these compounds, with the strength of the exchange decreasing down the halide series. Ac magnetic susceptibility data further reveal all compounds to exhibit slow magnetic relaxation under zero dc field. In 1-I, which exhibits particularly weak exchange, magnetic relaxation occurs via a Raman mechanism associated with the individual uranium(III) centers. In contrast, for 1-Br and 1-Cl, magnetic relaxation occurs via an Orbach mechanism, likely involving relaxation between ground and excited exchange-coupled states. Significantly, in the case of 1-Cl, magnetic relaxation is sufficiently slow such that open magnetic hysteresis is observed up to 2.75 K, and the compound exhibits a 100-s blocking temperature of 2.4 K. This compound provides the first example of magnetic blocking in a compound containing only actinide-based ions, as well as the first example involving the uranium(III) oxidation state.

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Section: Resultsmentioning

confidence: 99%

Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp^iPr5)₃U₃X₆ (X = Cl, Br, I) Clusters

Lussier,

Ito,

McClain

et al. 2024

J. Am. Chem. Soc.

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Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides

Hsueh,

Barluzzi,

Rajeshkumar

et al. 2024

Dalton Trans.

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Rational (supra)molecular design and catalytic activity of cage-like Cu₄-based phenylsilsesquioxanes

Zueva,

Bilyachenko,

Khrustalev

et al. 2024

Nanoscale

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A trinuclear metallasilsesquioxane of uranium(iii)

Abstract: The silsesquioxane ligand (iBuPOSSH3) allowed the assembly of robust polynuclear complexes of uranium(iii) and the isolation of the first trinuclear U(iii) complex that exhibits magnetic exchange.

Cited by 3 publications

References 50 publications

Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp^iPr5)₃U₃X₆ (X = Cl, Br, I) Clusters

Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp^iPr5)₃U₃X₆ (X = Cl, Br, I) Clusters

Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides

Rational (supra)molecular design and catalytic activity of cage-like Cu₄-based phenylsilsesquioxanes

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A trinuclear metallasilsesquioxane of uranium(iii)

Abstract: The silsesquioxane ligand (iBuPOSSH3) allowed the assembly of robust polynuclear complexes of uranium(iii) and the isolation of the first trinuclear U(iii) complex that exhibits magnetic exchange.

Cited by 3 publications

References 50 publications

Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (CpiPr5)3U3X6 (X = Cl, Br, I) Clusters

Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (CpiPr5)3U3X6 (X = Cl, Br, I) Clusters

Synthesis, structure and redox properties of single-atom bridged diuranium complexes supported by aryloxides

Rational (supra)molecular design and catalytic activity of cage-like Cu4-based phenylsilsesquioxanes

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Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp^iPr5)₃U₃X₆ (X = Cl, Br, I) Clusters

Metal–Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (Cp^iPr5)₃U₃X₆ (X = Cl, Br, I) Clusters

Rational (supra)molecular design and catalytic activity of cage-like Cu₄-based phenylsilsesquioxanes