2013
DOI: 10.1021/ic401548a
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Topochemical Cross-Linking of the [Hf2N2] Layers with Sulfur in α-HfNBr

Abstract: α-HfNBr (space group Pmmn) isostructural with FeOCl consists of orthorhombic [Hf2N2] layers sandwiched by bromide layers. By the reaction with Na2S at 750 °C in a sealed glass tube, the α-type [Hf2N2] layers are topochemically cross-linked with sulfur to form α-Hf2N2S with a mutual shift of the layers in the ab plane by (a/2 + b/2) to crystallize in space group Immm and the lattice parameters a = 4.1422(1), b = 3.5058(1), and c = 11.4043(3) Å. At a higher reaction temperature of 850 °C, the β-type layered vari… Show more

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Cited by 7 publications
(5 citation statements)
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“…Sc 2 O 2 (CN 2 ) crystallizes with the same space group ( Immm ) as α‐Hf 2 N 2 S in which [N=C=N] 2– ions are substituted for S 2– , revealing the pseudo‐chalcogenide character of carbodiimide. The infrared spectroscopic data of Sc 2 O 2 (CN 2 ) also confirm the carbodiimide unit ([N=C=N] 2– ) instead of a cyanamide unit ([N≡C–N] 2– ).…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Sc 2 O 2 (CN 2 ) crystallizes with the same space group ( Immm ) as α‐Hf 2 N 2 S in which [N=C=N] 2– ions are substituted for S 2– , revealing the pseudo‐chalcogenide character of carbodiimide. The infrared spectroscopic data of Sc 2 O 2 (CN 2 ) also confirm the carbodiimide unit ([N=C=N] 2– ) instead of a cyanamide unit ([N≡C–N] 2– ).…”
Section: Resultsmentioning
confidence: 99%
“…The [M 2 O 2 ] 2+ layers in Sc 2 O 2 (CN 2 ) are closely related to those in tetragonal structures such as Bi 2 O 2 (CN 2 ) and La 2 O 2 (CN 2 ), however with mutual shifts with layers of [NCN] 2– ions. A conversion of the structure of Sc 2 O 2 (CN 2 ) into the structure of α‐Hf 2 N 2 S can be imagined by substitution the [NCN] 2– ion versus S 2– , emphasizing the carbodiimide as a pseudo‐chalcogenide ion.…”
Section: Discussionmentioning
confidence: 99%
“…Indeed, metathesis reactions have successfully introduced chalcogen anions in between the host cationic slabs, resulting in [Hf 2 N 2 ] 2 + [S 2 − ] from [Hf 2 N 2 ] 2+ [Cl − ] 2 and Ti 3 C 2 Ch (Ch = S, Te) from Ti 3 C 2 Br 2 MXene. 102,103 While these examples did not involve anionic redox, this alternative driving force may provide an opportunity to expand the applicability of chalcogen (de)intercalation beyond the oA-Ln 2 O 2 S 2-x system described in Figure 9. Structure characterization is another major challenge in anionic redox topochemistry.…”
Section: Characterizationsmentioning
confidence: 99%
“…These reactions can therefore serve as a driving force for introducing chalcogen-chalcogen bonds in a topochemical manner. Indeed, metathesis reactions have successfully introduced chalcogen anions in between the host cationic slabs, resulting in [Hf 2 N 2 ] 2+ [S 2– ] from [Hf 2 N 2 ] 2+ [Cl – ] 2 and Ti 3 C 2 Ch (Ch = S, Te) from Ti 3 C 2 Br 2 MXene. , While these examples did not involve anionic redox, this alternative driving force may provide an opportunity to expand the applicability of chalcogen (de)­intercalation beyond the oA -Ln 2 O 2 S 2‑x system described in Figure .…”
Section: Perspectives In Syntheses and Characterizationsmentioning
confidence: 99%
“…Compared to the development of topochemical reactions for oxides, examples involving nitrides still remain mostly unreported. To date, only a few successful topochemical cases have been reported to yield several interesting compounds, including the layered nitride LaReN 2 , [6] oxynitride EuTiO 2 N, [7] nitride hydride Sr 2 NH, [8] nitride halides such as M 2 NX (M = Ca, Sr, Ba), [9] and the nitride chalcogenides α-Zr 2 N 2 S, α-Hf 2 N 2 S. [10,11] Most topochemical reactions have their products/starting materials in the same or related symmetry. Here, we found a topochemical hydrogen intercalation involving a rotational structural transformation from orthorhombic Ca 3 CrN 3 (o-Ca 3 CrN 3 ) to hexagonal antiperovskite Ca 3 CrN 3 H (h-Ca 3 CrN 3 H).…”
mentioning
confidence: 99%