Cs[FeSe2], Cs3[FeSe2]2, and Cs7[Fe4Se8]: Missing Links of Known Chalcogenido Ferrate Series

Stüble, Pirmin; Röhr, Caroline

doi:10.1002/zaac.201700263

Cited by 13 publications

(8 citation statements)

References 57 publications

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“…The atomic coordinates and displacement parameters are listed in the supplementary material (Tables S1-S10). As all of these compounds are isotypic, no significant changes in the crystal structures like in the related thioferrates can be observed [16][17][18] Furthermore, due to the relatively low degree of substitution, no significant changes in the bond distances d(Ga-Q) and angles <Q-Ga-Q in the anionic chains are observed, i.e., all calculated distances and angles vary in a range smaller than three times the e.s.d.s. The mixed occupancies of the alkali metal sites and their large displacement parameters, prevents reasonable conclusions concerning any changes of the alkali metal coordination.…”

Section: Structure Refinement Of New Cs 1-x M X Gaq 2 -Mc16 (M = K Rmentioning

confidence: 91%

Influence of Alkali Metal Substitution on the Phase Transition Behavior of CsGaQ2 (Q = S, Se)

et al. 2017

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Abstract:The formation of solid solution series Cs 1−x M x GaQ 2 -mC64 (M = K, Rb; Q = S, Se; x = 0-1) was studied by X-ray diffraction and spectroscopic methods, revealing a complete miscibility of CsGaQ 2 -mC64 with RbGaQ 2 and KGaSe 2 , and a large miscibility gap with KGaS 2 . All solid solution members exhibit similar Raman spectra, indicating the covalent Ga-Q bonding character. The similar optical band gaps likewise further contribute to this conclusion. Up to a certain degree of substitution, these solid solutions undergo a phase transition similar to CsGaQ 2 -mC64. The influence of the substitution parameter x on phase transition process was investigated in situ using high-temperature X-ray powder diffraction experiments. Phase-pure solid solutions of the high-temperature polymorphs Cs 1−x M x GaQ 2 -mC16 were obtained up to x max (K) = 0.1 and x max (Rb) = 0.3. The crystal structures of these new CsGaQ 2 -mC16 analogous high-temperature phases were refined from synchrotron diffraction data by Rietveld-refinement.

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Section: Structure Refinement Of New Cs 1-x M X Gaq 2 -Mc16 (M = K Rmentioning

confidence: 91%

Influence of Alkali Metal Substitution on the Phase Transition Behavior of CsGaQ2 (Q = S, Se)

et al. 2017

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“…Particularly the A ‐rich compounds of this type, which exhibit isolated metallate building blocks, are interesting in several respects, even though they are difficult to prepare and handle: Salts containing Fe 4 Q 4 clusters, which are model compounds for much more complex systems, like e.g. the ferredoxins, are only observed with the larger countercations K + , Rb + and Cs + . Also only with these heavier alkali elements, oxido diferrates(III) like e.g.…”

Section: Introductionmentioning

confidence: 99%

“…the ferredoxins, [6] are only observed with the larger countercations K + , Rb + and Cs + . [7][8][9][10] Also only with these heavier alkali This structure-chemical relation to the h.c.p. packing, which is similarly found for most of the sodium dimetallates (e.g.…”

Section: Introductionmentioning

confidence: 99%

K₆In₂Q₆ (Q = S, Se, Te): Missing Links in the Series of Alkali Chalcogenido Ditrielates(III)

Langenmaier

Wissinger

Röhr

2019

Zeitschrift anorg allge chemie

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The chalcogenido indates K6In2Q6 (Q = S, Se, Te) were synthesized from melts of the pure elements at a maximum temperature of 700 °C. All three potassium salts contain dinuclear units [In2Q6]6– of two edge‐sharing [InQ4] tetrahedra. The sulfido and the selenido indate are isotypic and crystallize in the K6Mn2O6‐type structure [monoclinic, space group P21/c, a = 784.32(9)/809.32(3), b = 1274.58(14)/1322.37(4), c = 836.48(9)/870.53(3) pm, β = 97.900(2)/97.5877(8)°, Z = 2, R1 = 0.0123/0.0109; for Q = S/Se]. The tellurido indate K6In2Te6 crystallizes in a new orthorhombic structure type [space group Pnma, a = 1793.70(12), b = 1491.55(11), c = 837.40(6) pm, Z = 4, R1 = 0.0157]. In this structure, the telluride anions form a hexagonal close packing, in which K+ cations occupy all octahedral voids; the In3+ ions take 1/6 (but always adjacent) tetrahedral voids. This structure‐chemical relation to the h.c.p. packing, which is similarly found for most of the sodium dimetallates (e.g. Na6Fe2S6), is substantiated by a full crystallographic group‐subgroup tree. The crystal chemistry of the new indates is discussed and compared with that of alkali chalcogenido metallates(III) of Fe, Al and Ga containing [M2Q6]6– dimers, which overall form as many as ten different structure types. DFT band structure calculations of the three title compounds exhibit bandgaps, which continuously decrease from the S to the Te compound and which are also in accordance with the pale yellow (S), bright yellow (Se) and red‐brown (Te) color of the compounds. The chemical bonding in the salts and within the metallate anion is discussed on the basis of the partial DOS and a Bader analysis of the calculated electron density.

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“…[6] Although examples for such sulfido ferrate(II/III) salts are long known [7][8][9] and some occur even naturally, [10,11] new A-rich compounds could recently be crystallized from melts using the elemental alkali metals as starting materials. This comprises members of the family of chain/cluster compounds A 3 Fe 2 Q 4 /A 6-7 Fe 4 Q 8 ( [3,[12][13][14][15] and references cited therein) and the magnetically unusual, i.e. valence-delocalized FM, sodium diferrate Na 7 [Fe 2 S 6 ].…”

Section: Introductionmentioning

confidence: 99%

K₅[InSe₄] and K₁₂[InS₄]₂(S): New Alkali Chalcogenido Indates with [InQ₄]⁵^–ortho Anions

Langenmaier

Wissinger

Röhr

2020

Zeitschrift anorg allge chemie

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The new chalcogenido ortho indates(III) K 5 [InSe 4 ] and K 12 [InS 4 ] 2 (S) were synthesized from melts of the elements (Se) [or with S/In 2 S 3 as chalcogen source] at maximum temperatures of 700/ 800°C. The two potassium salts, which were characterized by means of X-ray single crystal structure analysis, contain isolated tetrahedral ortho anions [InQ 4 ] 5-. K 5 [InSe 4 ] crystallizes in a new structure type [monoclinic, space group C2/c, a = 2014.2(2), b = 1553.1(2), c = 1661.1(2) pm, β = 94.716(2)°, Z = 16, R 1 = 0.0317]. The complex structure contains two crystallographically different [InSe 4 ] 5tetrahedra [d(In•••Se) = 254.3-263.6 pm], which are arranged into 4 4 [In(1), A] and 3 2 .4.3.4 [In(2), B] nets. These nets are |:ABAЈBЈ:| stacked along the a axis. The 11 crystallographically independent K + ions are coordinated by four (1ϫ), five (3ϫ) and six (7ϫ) selenido anions [d(K-Se) = 309-415 pm]. The crystal structure and the calculated electronic structure of the pure ortho indate K 5 [InSe 4 ] are compared with the known "double salts" K 9 [InSe 4 ] 2 (Se) and K 9 [InSe 4 ](Se 2)(Se),

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Cs[FeSe₂], Cs₃[FeSe₂]₂, and Cs₇[Fe₄Se₈]: Missing Links of Known Chalcogenido Ferrate Series

Cited by 13 publications

References 57 publications

Influence of Alkali Metal Substitution on the Phase Transition Behavior of CsGaQ2 (Q = S, Se)

Influence of Alkali Metal Substitution on the Phase Transition Behavior of CsGaQ2 (Q = S, Se)

K₆In₂Q₆ (Q = S, Se, Te): Missing Links in the Series of Alkali Chalcogenido Ditrielates(III)

K₅[InSe₄] and K₁₂[InS₄]₂(S): New Alkali Chalcogenido Indates with [InQ₄]⁵^–ortho Anions

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Cs[FeSe2], Cs3[FeSe2]2, and Cs7[Fe4Se8]: Missing Links of Known Chalcogenido Ferrate Series

Cited by 13 publications

References 57 publications

Influence of Alkali Metal Substitution on the Phase Transition Behavior of CsGaQ2 (Q = S, Se)

Influence of Alkali Metal Substitution on the Phase Transition Behavior of CsGaQ2 (Q = S, Se)

K6In2Q6 (Q = S, Se, Te): Missing Links in the Series of Alkali Chalcogenido Ditrielates(III)

K5[InSe4] and K12[InS4]2(S): New Alkali Chalcogenido Indates with [InQ4]5–ortho Anions

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Cs[FeSe₂], Cs₃[FeSe₂]₂, and Cs₇[Fe₄Se₈]: Missing Links of Known Chalcogenido Ferrate Series

K₆In₂Q₆ (Q = S, Se, Te): Missing Links in the Series of Alkali Chalcogenido Ditrielates(III)

K₅[InSe₄] and K₁₂[InS₄]₂(S): New Alkali Chalcogenido Indates with [InQ₄]⁵^–ortho Anions