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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
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The structure-directing amine changes everything: structures and optical properties of two-dimensional thiostannates
Mette Ø Filsø1, Iman Chaaban2, Amer Al Shehabi2
1Center for Materials Crystallography, Department of Chemistry and iNANO, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
Summary
Two novel two-dimensional thiostannates (SnS) were synthesized, exhibiting distinct optical properties due to structural differences. These semiconducting materials offer insights into structure-property relationships in layered tin sulfides.
Area of Science:
- Materials Science
- Solid-State Chemistry
- Inorganic Synthesis
Background:
- Two-dimensional (2D) materials, including thiostannates (SnS), are of significant interest for their unique electronic and optical properties.
- The R-SnS-1 family represents a class of layered SnS compounds with potential applications in semiconductor technology.
- Understanding the relationship between crystal structure and optoelectronic properties is crucial for designing new materials.
Purpose of the Study:
- To synthesize and characterize two new 2D thiostannates using different structure-directing agents: tris(2-aminoethyl)amine (tren) and 1-(2-aminoethyl)piperidine (1AEP).
- To investigate the structural origins of the observed differences in the band gaps of the synthesized SnS compounds.
- To explore the cation-layer interactions within the 1AEP-SnS-1 structure.
Main Methods:
- Synthesis of two distinct 2D thiostannates using tren and 1AEP as structure-directing agents.
- Detailed structural analysis employing X-ray diffraction, solid-state 13C and 119Sn MAS NMR spectroscopy, and scanning electron microscopy.
- Hirshfeld surface analysis to probe cation-layer interactions in the 1AEP-SnS-1 compound.
Main Results:
- Two different 2D thiostannates, tren-SnS-1 (hexagonal, planar layers) and 1AEP-SnS-1 (orthorhombic, non-planar layers), were successfully synthesized.
- Despite sharing identical fundamental building units (Sn3S4 clusters), the compounds exhibit significantly different band gaps (2.96 eV for tren-SnS-1 and 3.21 eV for 1AEP-SnS-1).
- 1AEP-SnS-1 formation involves an intramolecular reaction of the piperidine cation via C-H activation, leading to ordered cations and distorted layers.
Conclusions:
- The structural differences, specifically the planarity of SnS layers and cation ordering, are responsible for the distinct optical properties (band gaps) of tren-SnS-1 and 1AEP-SnS-1.
- The study highlights the critical role of structure-directing agents in controlling the dimensionality and properties of layered inorganic materials.
- Hirshfeld analysis reveals specific sulfur bridge interactions as the most nucleophilic sites in the 1AEP-SnS-1 structure.
Keywords:
Hirshfeld surface analysislight absorptionsingle-crystal diffractionsolid-state NMR spectroscopysolvothermal synthesistwo-dimensional thiostannatesMore Related Videos
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