Non-innocent Intercalation of Diamines into Tetragonal FeS Superconductor

Harmer, Colin P.; Pak, Chongin; Greenfield, Joshua T.; Adeyemi, Adedoyin N.; Gamage, Eranga H.; Kovnir, Kirill

doi:10.1021/acsaem.0c02996

Cited by 11 publications

(37 citation statements)

References 27 publications

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“…This curvature is of similar magnitude to that previously evident in thin mackinawite crystallites . Undulations of FeS layers have also been linked to vacancies in the layer; − vacancies and nonstoichiometries such as these have been shown to dramatically impact electronic properties . Models for these nonstoichiometric phases, with ordered vacancies and undulations, did not yield good fits to the PDF data.…”

supporting

confidence: 71%

Resolving Single-layer Nanosheets as Short-lived Intermediates in the Solution Synthesis of FeS

Beauvais

Chupas

O’Nolan

et al. 2021

ACS Materials Lett.

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Short-lived reaction intermediates play a critical role in mediating material synthesis. Such short-lived species often elude characterization because of the mismatch between the time scale of measurements capable of describing them and their lifetimes. Thus, we have limited ability to probe, understand, and control the mechanism for material synthesis.Here we demonstrate a new approach to in situ X-ray pair distribution function (PDF) measurements of dynamic nanomaterials structure that yields an unprecedented combination of reaction time resolution and sensitivity. Reaction time is resolved spatially as a function of position along a flow path. By applying this approach to the well-studied aqueous reaction leading to FeS, mackinawite, we identify a novel metastable intermediate, FeS layer , that forms in the first second of the reaction and which can be described as individual FeS nanosheets. Recognizing these nanosheets as synthons in the reaction opens up the possibility to deliberately redirect this assembly of the nanosheet toward different phases, including novel heterostructures.

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supporting

confidence: 71%

Resolving Single-layer Nanosheets as Short-lived Intermediates in the Solution Synthesis of FeS

Beauvais

Chupas

O’Nolan

et al. 2021

ACS Materials Lett.

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“…Neutron diffraction studies are hampered by the high cost of commercial deuterated d 8 -ethylenediamine given the amounts required for solvothermal experiments. 17 As a result, the FeCh layer can be reasonably modeled by powder X-ray diffraction but any intercalate structure can be thought of as a more qualitative, schematic picture, where many solutions can fit the data. Overall, the total Fe:Ch ratio is noted as a significant parameter defining magnetic and/or superconducting properties as it was directly related to the stoichiometry of the Fe-Ch tetrahedral layer and used to evaluate whether any Fe vacancies are present.…”

Section: ■ Introductionmentioning

confidence: 99%

“…11,18 Moreover, we have shown that ethylenediamine is capable of leaching Fe from the stoichiometric FeS layers to form [Fe(en) 3 ] 2+ in situ. 17 The absence of high-quality crystal structure data due to the low crystallinity of the intercalated phases together with potential disorder in the interlayer space and Fe vacancies in the Fe-Ch layers prevent the development of structure−property relationships for this class of compounds. To better pinpoint the causes for the observed range of property changes, it is crucial to not only know the structure but also systematically alter the structure and composition to better relate the structure and properties.…”

Section: ■ Introductionmentioning

confidence: 99%

Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species

et al. 2022

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Systematic synthesis studies of the formation of tetrahedral FeSethylenediamine intercalates resulted in the synthesis of a new compound, [Fe 9.4(2) S 10 ][Fe(en) 3 ] 0.6(1) •en 0.9(3) . The composition and complex crystal structure were determined based on a synergistic combination of elemental composition, decomposition behavior, high-resolution synchrotron X-ray diffraction and total scattering, 57 Fe Mossbauer spectroscopy, and electron diffraction. The structural model was derived based on a systematic comparison to the previously reported structures [Fe 8 S 10 ][Fe(en) 3 ] 1 •en 0.5 and tetragonal FeS. The new compound has flat Fe 9.4 S 10 layers, analogous to those in superconducting binary FeS. In the crystal structure of [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 •en 0.9 , the interlayer space is occupied by [Fe(en) 3 ] 2+ complexes and neutral ethylenediamine molecules in a ∼2:3 ratio. Interlayer species are not randomly oriented but ordered as evidenced by superstructural diffraction peaks in both high-resolution Xray diffraction and electron diffraction patterns. Magnetic studies reveal no superconducting transition down to 2 K, indicating that the presence of minute amounts (∼6%) of iron vacancies at the Fe-S layer in [Fe 9.4 S 10 ][Fe(en) 3 ] 0.6 •en 0.9 is still sufficient to shift the position of the Fermi level resulting in an adjustment of the properties. Our work shows the importance of detailed characterization of the crystal structure of intercalated compounds to understand the origin of the observed properties and develop proper structure− property relationships.

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“…Recently, Kovnir et al have demonstrated that [Fe(en) 3 ] 2+ complexes can intercalate along with neutral en molecules in layered iron sulfides related to superconductors. 55 The classic Werner complex [Co(en) 3 ] 3+ is chiral, which arises from the bidentate nature of the chelating en ligand. We note that our complexes are slightly different from that of Werner since ours contain divalent Co (d 7 ), whereas those studied by Werner were trivalent Co (d 6 ).…”

Section: ■ Discussionmentioning

confidence: 99%

“…The work of Bensch − and Dai − has demonstrated how such coordination complexes can act as structure-directing agents for inorganic semiconductors. Recently, Kovnir et al have demonstrated that [Fe(en) 3 ] 2+ complexes can intercalate along with neutral en molecules in layered iron sulfides related to superconductors …”

Section: Discussionmentioning

confidence: 99%

Polar Ferromagnetic Metal by Intercalation of Metal–Amine Complexes

et al. 2021

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The metal−amine complex Co(en) 3 , where en = ethylenediamine, intercalates between layers of cobalt sulfide (CoS) to form a polar, ferromagnetic metal. We solve the structure of the hybrid compound [Co(en) 3 ](CoS) 12 •en in the polar group Pca2 1 with lattice parameters a = 14.778(3) Å, b = 11.066(3) Å, and c = 20.095(5) Å using single-crystal X-ray diffraction. The [Co(en) 3 ] 2+ complexes order between CoS layers and break their inherent fourfold symmetry. Moreover, the chiral Co(en) 3 complexes hydrogen bond to the terminal sulfides of the layers and break inversion symmetry, thereby inducing a polar state. The shortest hydrogen bond of the amino group is H•••S = 2.41(1) Å. From 1.8 to 300 K, the title compound displays metallic electrical resistivity and an anomaly at 43 K. Through magnetization measurements, we find that Co(en) 3 exhibits spontaneous ferromagnetic order below 43 K. First-principles calculations reproduce the ferromagnetic structure and illustrate decoupling between the conducting electrons and the inversion-lifting distortion. Our work shows that hybrid materials created from intercalation chemistry of functional 2D hosts provides a pathway for uniting contraindicated properties.

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Non-innocent Intercalation of Diamines into Tetragonal FeS Superconductor

Cited by 11 publications

References 27 publications

Resolving Single-layer Nanosheets as Short-lived Intermediates in the Solution Synthesis of FeS

Resolving Single-layer Nanosheets as Short-lived Intermediates in the Solution Synthesis of FeS

Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species

Polar Ferromagnetic Metal by Intercalation of Metal–Amine Complexes

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