Ca54In13B4–xH23+x: A Complex Metal Subhydride Featuring Ionic and Metallic Regions

Blankenship, Trevor V.; Chen, Banghao; Latturner, Susan E.

doi:10.1021/cm5007982

Cited by 10 publications

(18 citation statements)

References 53 publications

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“…There is also a signal at around 4 ppm observed in the 2 H NMR spectrum that was reported before and assigned to decomposition products [56]. This is in agreement with our observations: the signal clearly belongs to the sample as it is observed in the 2 H MAS spectrum of the deuterated substance and in addition, while being hardly observable shortly after synthesis (as can be seen in the 1 H NMR spectra) the signal grows in integrated intensity after several weeks.…”

Section: Nmr: Local Information On the Hydride Ionssupporting

confidence: 92%

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The ‘sub’ metallide oxide hydrides Sr21Si2O5H

Jehle

Hoffmann

Kohlmann

et al. 2015

Journal of Alloys and Compounds

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Section: Nmr: Local Information On the Hydride Ionssupporting

confidence: 92%

“…(In contrast, other H À containing metallides like Ba 9 In 4 H [40] or Ca 54 In 13 B 4Àx H 23þx [56] exhibit no alkaline-earth rich structure regions and are thus better compared to the family of simple metallide oxides, like e.g. Ba 3 SnO).…”

Section: Chemical Bondingmentioning

confidence: 99%

The ‘sub’ metallide oxide hydrides Sr21Si2O5H

Jehle

Hoffmann

Kohlmann

et al. 2015

Journal of Alloys and Compounds

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“…The metal flux has proven to be a powerful tool for growing large (millimeter scale), high-quality single crystals that are suitable for property measurements. ,,,− Here, we utilized liquid indium to dissolve both iridium metal and the chalcogen of interest to access three different isostructural compounds Ir 2 In 8 Q as large crystals and thereby demonstrate the potential to synthesize subchalcogenides with this method. Scanning electron microscopy (SEM) and semiquantitative energy-dispersive spectroscopy (EDS) for the newly reported Ir 2 In 8 Se and Ir 2 In 8 Te can be seen in Figures S1 and S2.…”

Section: Results and Discussionmentioning

confidence: 99%

The Subchalcogenides Ir₂In₈Q (Q = S, Se, Te): Dirac Semimetal Candidates with Re-entrant Structural Modulation

et al. 2020

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Subchalcogenides are uncommon compounds where the metal atoms are in unusually low formal oxidation states. They bridge the gap between intermetallics and semiconductors, and can have unexpected structures and properties because of the exotic nature of their chemical bonding, as they contain both metal-metal and metal-main group (e.g. halide, chalcogenide) interactions.Finding new members of this class of materials presents synthetic challenges, as attempts to make them often result in phase separation into binary compounds. We overcome this difficulty by utilizing indium as a metal flux to synthesize large (mm scale) single crystals of novel subchalcogenide materials. Herein, we report two new compounds Ir 2 In 8 Q (Q = Se, Te) and compare their structural and electrical properties to the previously reported Ir 2 In 8 S analogue.Ir 2 In 8 Se and Ir 2 In 8 Te crystallize in the P4 2 /mnm space group and are isostructural to Ir 2 In 8 S but also have commensurately modulated (with q-vectors q = 1/6a* + 1/6b* and q= 1/10a* + 1/10b* for Ir 2 In 8 Se and Ir 2 In 8 Te, respectively) low temperature phase transitions, where the chalcogenide anions in the channels experience a distortion in the form of In-Q bond alternation along the ab plane. Both compounds display re-entrant structural behavior, where the supercells appear on cooling but revert to the original subcell below 100 K, suggesting competing structural and electronic interactions dictate the overall structure. Notably, these materials are topological semimetal candidates with symmetry-protected Dirac crossings near the Fermi level, and exhibit high electron mobilities (~1500 cm 2 V -1 s -1 at 1.8 K) and moderate carrier concentrations (~10 20 cm -3 ) from charge transport measurements. This work highlights metal flux as a powerful synthetic route to high quality single crystals of novel intermetallic subchalcogenides.

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“…This hydride band is higher in energy than is typically seen for calcium-based hydrides such as Ca 54 In 13 B 4−x H 23+x , LiCa 2 C 3 H, and LiCa 3 As 2 H, all of which have their hydride states 4 eV below the Fermi level. 11,13,14 This may reflect the longer distance between the H − anion and surrounding Ba 2+ cations in Ba 12 InC 18 H 4 , which would lead to a weaker interaction. A very small integrated COHP value of 0.37 eV/cell for the Ba−H interaction confirms the weak nature of the bonding (see Table S3 in the SI).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Ca₁₂InC_13–x and Ba₁₂InC₁₈H₄: Alkaline-Earth Indium Allenylides Synthesized in AE/Li Flux (AE = Ca, Ba)

et al. 2014

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Two new complex main-group metal carbides were synthesized from reactions of indium, carbon, and a metal hydride in metal flux mixtures of an alkaline earth (AE = Ca, Ba) and lithium. Ca(12)InC(13-x) and Ba(12)InC(18)H(4) both crystallize in cubic space group Im3̅ [a = 9.6055(8) and 11.1447(7) Å, respectively]. Their related structures are both built on a body-centered-cubic array of icosahedral clusters comprised of an indium atom and 12 surrounding alkaline-earth cations; these clusters are connected by bridging monatomic anions (either H(-) or C(4-)) and allenylide anions, C(3)(4-). The allenylide anions were characterized by Raman spectroscopy and hydrolysis studies. Density of states and crystal orbital Hamilton population calculations confirm that both compounds are metallic.

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Ca₅₄In₁₃B_4–xH_23+x: A Complex Metal Subhydride Featuring Ionic and Metallic Regions

Abstract: Table S1. Atom positions and isotropic thermal parameters for Ca 52.7 In 13 B 1.6 H 25.4 (crystal 1) Wyckoff Site x y z occ U eq a

Cited by 10 publications

References 53 publications

The ‘sub’ metallide oxide hydrides Sr21Si2O5H

The ‘sub’ metallide oxide hydrides Sr21Si2O5H

The Subchalcogenides Ir₂In₈Q (Q = S, Se, Te): Dirac Semimetal Candidates with Re-entrant Structural Modulation

Ca₁₂InC_13–x and Ba₁₂InC₁₈H₄: Alkaline-Earth Indium Allenylides Synthesized in AE/Li Flux (AE = Ca, Ba)

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Ca54In13B4–xH23+x: A Complex Metal Subhydride Featuring Ionic and Metallic Regions

Abstract: Table S1. Atom positions and isotropic thermal parameters for Ca 52.7 In 13 B 1.6 H 25.4 (crystal 1) Wyckoff Site x y z occ U eq a

Cited by 10 publications

References 53 publications

The ‘sub’ metallide oxide hydrides Sr21Si2O5H

The ‘sub’ metallide oxide hydrides Sr21Si2O5H

The Subchalcogenides Ir2In8Q (Q = S, Se, Te): Dirac Semimetal Candidates with Re-entrant Structural Modulation

Ca12InC13–x and Ba12InC18H4: Alkaline-Earth Indium Allenylides Synthesized in AE/Li Flux (AE = Ca, Ba)

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Ca₅₄In₁₃B_4–xH_23+x: A Complex Metal Subhydride Featuring Ionic and Metallic Regions

The Subchalcogenides Ir₂In₈Q (Q = S, Se, Te): Dirac Semimetal Candidates with Re-entrant Structural Modulation

Ca₁₂InC_13–x and Ba₁₂InC₁₈H₄: Alkaline-Earth Indium Allenylides Synthesized in AE/Li Flux (AE = Ca, Ba)