Reaction of Ni2+ and SnS as a Way to Form Ni@SnS and Sn2Ni3S2 Nanocrystals: Control of Product Formation and Shape

Rommel, Stefan Michael; Weihrich, Richard

doi:10.1002/chem.201500498

“…Crystal and electronic structure calculations were performed with the CRYSTAL14 code. , GGA (PBE) and LDA as well as implemented hybrid (B3LYP, PBE0) functionals were applied. All electron basis sets for Sn, Ni, and S were taken from previous calculations on Ni 3 Sn 2 S 2 -type compounds (see literature − ); for N, C, and H the electron basis sets were taken from online resources [see Supporting Information]. For crystal structure predictions atomic positions were relaxed according to the implemented Schlegel-type algorithm.…”

Section: Methodsmentioning

confidence: 99%

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]₂[Sn₂S₆]}_n

Hilbert

¹

,

Näther

²

,

Weihrich

³

et al. 2016

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The compound {[Ni(tren)]2[Sn2S6]}n (1) (tren = tris(2-aminoethyl)amine, C6H18N4) was successfully applied as source for the room-temperature synthesis of the new thiostannates [Ni(tren)(ma)(H2O)]2[Sn2S6]·4H2O (2) (ma = methylamine, CH5N) and [Ni(tren)(1,2-dap)]2[Sn2S6]·2H2O (3) (1,2-dap = 1,2-diaminopropane, C3H10N2). The Ni-S bonds in the Ni2S2N8 bioctahedron in the structure of 1 are analyzed with density functional theory calculations demonstrating significantly differing Ni-S bond strengths. Because of this asymmetry they are easily broken in the presence of an excess of ma or 1,2-dap immediately followed by Ni-N bond formation to N donor atoms of the amine ligands thus generating [Ni(tren)(amine)](2+) complexes. The chemical reactions are fast, and compounds 2 and 3 are formed within 1 h. The synthesis concept presented here opens hitherto unknown possibilities for preparation of new thiostannates.

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“…Along the line AX+M, bulk powders of cubic PbS and orthorhombic SnS can be transformed with Ni at elevated temperatures ( T >400 °C, path 1) in pure solid‐state reactions into trigonal‐layered shandite‐type Ni 3 Pb 2 S 2 and isotypic Ni 3 Sn 2 S 2 . This path is also used under mild conditions ( T =166–197 °C) from SnS and PbS nanoparticles in a reductive solution of Ni 2+ . A diffusion‐driven mechanism was proven for the formation of the ternaries, whereas core‐shell particles Ni@SnS are formed by a more rapid reduction.…”

Section: Resultsmentioning

confidence: 99%

“…A diffusion‐driven transformation was concluded similar to the conversion of PbS to Ni 3 Pb 2 S 2 . In both cases, binary chalcogenide precursors AX are converted to perovskite‐related M 3 A 2 X 2 =M 1.5 AX compounds by adding the transition‐metal Ni. As from solid‐state reactions pyrite‐type PtSnS is formed from SnS+Pt, hypothetical “NiAX” was computed from total‐energy DFT calculations.…”

Section: Introductionmentioning

confidence: 84%

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Conversion Reactions of Solids: From a Surprising Three‐Step Mechanism towards Directed Product Formation

Rommel

¹

,

Krach

²

,

Peter

³

et al. 2016

Chemistry A European J

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Directed conversion reactions from binary to multinary compounds are discovered from the reaction of Bi2 S3 and Bi2 Se3 with NiCl2 ⋅6 H2 O in polyol media under basic conditions. Control of the synthesis conditions allows the preparation of NiBiSe and superconducting Ni3 Bi2 S2 and Ni3 Bi2 Se2 . The formation of Ni3 Bi2 S2 from Bi2 S3 is found from an unexpected three-step reaction path with Bi and NiBi as intermediates. In the more complex Ni/Bi/Se system, the mechanism found can be used to selectively direct the reaction between the competing ternaries and to suppress side-product formation. Contrary to solid-state reactions (500-900 °C) control of product formation is reached at reaction temperatures and times between 166-300 °C and 0.5-10 h, respectively. The formation of different phases is discussed from results of DFT calculations.

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From3DIntermetallic Antiperovskites to2DHalf Antiperovskites

Weihrich

¹

,

Köhler

²

,

Pielnhofer

³

et al. 2017

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The concept of ordered half antiperovskites (HAP) derives A 2 M 3 X 2 structures formally from metal‐rich intermetallic antiperovskites AM 3 X such as MgNi 3 C. It was developed within the last decade in Regensburg accompanied by fascinating discoveries of other groups. It extends the idea known for oxide structures related to perovskite such as cuprate superconductors: therein, the 3D M‐O network is cut to 2D sheets, that is YBaCu 2 O 7‐d . By systematic formation of unoccupied sites 3D interlinked MO 6 octahedra in perovskites are cut to 2D substructures with CuO 4 and CuO 5 units. To the best of our knowledge, a similar scheme was not described for antiperovskites AM 3 X, where X and M sites of perovskites are exchanged. MgNi 3 C is taken subsequently as reference example. First reported by Hütter and Stadelmaier it became famous as noncuprate nonoxide superconductor. We show that MX 6 and XM 6 units in perovskites AMX 3 and APs AM 3 X can be cut to MX 3 and XM 3 units to form 2D structures. The situation compares to gray As and black P that are derived from a primitive α‐Po structure by cutting three of the six bonds. In both cases, interlinked 3D networks are cut to 2D structures. However, the ternary compounds introduce additional degrees of freedom by varying the electron count by composition that turns out important to design properties such as for example magnetism and thermoelectrics of superconductivity. Consequently, the HAP concept consists of a crystal structure part for compounds A 2 M 3 X 2 = AM 3/2 L 3/2 X with AP superstructures and an electronic structure part. In this review, we point out relations to antiperovskite AM 3 X crystal and electronic structures, the history of A 2 M 3 X 2 compounds, the HAP concept, important discoveries of HAP materials and novel investigations on synthesis, spintronics, thermoelectrics, superconductors, and topological properties. Advantages of the given conceptual view are pointed out for computer modeling, design, and prediction of structures and functions.

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Reaction of Ni²⁺ and SnS as a Way to Form Ni@SnS and Sn₂Ni₃S₂ Nanocrystals: Control of Product Formation and Shape

Cited by 6 publications

References 41 publications

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]₂[Sn₂S₆]}_n

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]₂[Sn₂S₆]}_n

Conversion Reactions of Solids: From a Surprising Three‐Step Mechanism towards Directed Product Formation

From3DIntermetallic Antiperovskites to2DHalf Antiperovskites

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Reaction of Ni2+ and SnS as a Way to Form Ni@SnS and Sn2Ni3S2 Nanocrystals: Control of Product Formation and Shape

Cited by 6 publications

References 41 publications

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]2[Sn2S6]}n

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]2[Sn2S6]}n

Conversion Reactions of Solids: From a Surprising Three‐Step Mechanism towards Directed Product Formation

From3DIntermetallic Antiperovskites to2DHalf Antiperovskites

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Reaction of Ni²⁺ and SnS as a Way to Form Ni@SnS and Sn₂Ni₃S₂ Nanocrystals: Control of Product Formation and Shape

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]₂[Sn₂S₆]}_n

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]₂[Sn₂S₆]}_n