An [FeIII30] molecular metal oxide

Dearle, Alice E.; Cutler, Daniel J.; Coletta, Marco; Lee, Edward; Dey, Sourav; Sanz, Sergio; Fraser, Hector W. L.; Nichol, Gary S.; Rajaraman, Gopalan; Schnack, Jürgen; Cronin, Leroy; Brechin, Euan K.

doi:10.1039/d1cc06224g

Cited by 10 publications

(12 citation statements)

References 33 publications

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“…32d-f), 288,289 Fe 19 (Fig. 32j-l), 290 Fe 30 , 291 and Fe 34 (Fig. 32m-o) 292 ) were prepared, but also heterometal ions were used to capture and stabilize the basic motifs (like Bi 3+ -stabilized Bi 6 Fe 13 (Fig.…”

Section: Fe Clustersmentioning

confidence: 99%

Platonic and Archimedean solids in discrete metal-containing clusters

Luo

Dong

et al. 2023

Chem. Soc. Rev.

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Section: Fe Clustersmentioning

confidence: 99%

Platonic and Archimedean solids in discrete metal-containing clusters

Luo

Dong

et al. 2023

Chem. Soc. Rev.

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“…The first example was an Fe 10 wheel, and since then many others have been reported and now comprise a large family with various Fe x nuclearities. − They are also excellent model systems for the study of 1D magnetism and quantum effects, e.g., coherent tunneling . There are also a multitude of other Fe III /oxo clusters of various structural topologies, but it is surprising that very few of them possess an Fe nuclearity of >20. − This is an area where the creative development of new synthetic procedures for high-nuclearity Fe III /O clusters would be of great benefit, as they have been in Mn cluster chemistry where Mn 70 and Mn 84 oxo clusters have been known for many years. , …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Magnetic Properties of an Fe₃₆ Dimethylarsinate Cluster: The Largest “Ferric Wheel”

et al. 2022

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The synthesis and characterization of a high-nuclearity FeIII/O/arsinate cluster is reported within the salt [Fe36O12(OH)6(O2AsMe2)63(O2CH)3(H2O)6](NO3)12 (1). The compound was prepared from the reaction of Fe(NO3)3·9H2O, dimethylarsinic acid (Me2AsO2H), and triethylamine in a 1:2:4 molar ratio in acetonitrile. The Fe36 cation of 1 is an unprecedented structural type consisting of nine Fe4 butterfly units of two types, three {FeIII 4(μ3-O)2} units A, and six {FeIII 4(μ3-O)(μ3-OH)} units B, linked by multiple bridging Me2AsO2 – groups into an Fe36 triangular wheel/loop with C 3 crystallographic and D 3 virtual symmetry that looks like a guitar plectrum. The unusual structure has been rationalized on the basis of the different curvatures of units A and B, the presence of intra-Fe36 hydrogen bonding, and the tendency of Me2AsO2 – groups to favor μ3-bridging modes. The cations stack into supramolecular nanotubes parallel to the crystallographic c axis and contain badly disordered solvent and NO3 – anions. The cation of 1 is the highest-nuclearity “ferric wheel” to date and also the highest-nuclearity Fe/O cluster of any structural type with a single contiguous Fe/O core. Variable-temperature direct-current magnetic susceptibility data and alternating-current in-phase magnetic susceptibility data indicate that the cation of 1 possesses an S = 0 ground state and dominant antiferromagnetic interactions. The Fe2 pairwise J i,j couplings were estimated by the combined use of a magnetostructural correlation for high-nuclearity FeIII/oxo clusters and density functional theory calculations using broken-symmetry methods and the Green’s function approach. The three methods gave satisfyingly similar J i,j values and allowed the identification of spin-frustration effects and the resulting relative spin-vector alignments and thus rationalization of the S = 0 ground state of the cation.

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“…The striking structural similarties between the molecular iron oxides [Fe III 13 ], 12 [Fe III 17 ], 8,13 [Fe III 30 ], 14 and [Fe III 34 ] 15 which all possess alternating “layers” or tetrahedral and octahedral Fe III ions has prompted us to speculate, and examine, whether very large molecular iron oxides, perhaps even rivalling the size and complexity of the polyoxometalates, 16 can be isolated. The inability of Fe III to be stabilised by terminal oxide ions and the propensity of aqueous solutions of Fe III to produce mixtures of intractable/insoluble/amorphous solids suggests however that alternative synthetic pathways may have to be explored.…”

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confidence: 99%

“…13 Addition of different bases, templates and solvent combinations results in the formation of the related, but larger [Fe 30 ] and [Fe 34 ] clusters. 14,15 Herein, we extend this methodology to the use of 4-methoxypyridine (MeO-py) and the synthesis of the smallest member of this molecular iron oxide family, an [Fe 8 ] cage. Dissolution of FeBr 3 in MeO-py with stirring for 2.…”

mentioning

confidence: 99%