Guanidinium and Mixed Cesium–Guanidinium Tin(II) Bromides: Effects of Quantum Confinement and Out-of-Plane Octahedral Tilting

Hybrid organic–inorganic main-group metal halide compounds are the subject of intense research owing to their unique optoelectronic characteristics. In this work, we report the synthesis, structure, and electronic and optical properties of a family of hybrid tin (II) bromide compounds comprising gua...

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Bibliographic Details
Published in:Chemistry of materials 2019-03, Vol.31 (6), p.2121-2129
Main Authors: Nazarenko, Olga, Kotyrba, Martin R, Yakunin, Sergii, Wörle, Michael, Benin, Bogdan M, Rainò, Gabriele, Krumeich, Frank, Kepenekian, Mikaël, Even, Jacky, Katan, Claudine, Kovalenko, Maksym V
Format: Article
Language:English
Subjects:
Chemical Sciences
Material chemistry
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Summary:Hybrid organic–inorganic main-group metal halide compounds are the subject of intense research owing to their unique optoelectronic characteristics. In this work, we report the synthesis, structure, and electronic and optical properties of a family of hybrid tin (II) bromide compounds comprising guanidinium [G, C­(NH2)3 +] and mixed cesium–guanidinium cations: G2SnBr4, CsGSnBr4, and Cs2GSn2Br7. G2SnBr4 has a one-dimensional structure that consists of chains of corner-sharing [SnBr5]2– square pyramids and G cations situated in between the chains. Cs+ exhibits a pronounced structure-directing effect where a mixture of Cs+ and G cations forms mono- and bilayered two-dimensional perovskites: CsGSnBr4 and Cs2GSn2Br7. Furthermore, the flat shapes of the guanidinium cations induce anisotropic out-of-plane tilts of the [SnBr6]4– octahedra in the CsGSnBr4 and Cs2GSn2Br7 compounds. In G2SnBr4, the Sn lone pair is highly stereoactive and favors non-octahedral, that is, square pyramidal coordination of Sn­(II). G2SnBr4 exhibits bright broad-band emission from self-trapped excitonic states, owing to its soft lattice and electronic localization. This emission in G2SnBr4 is characterized by a photoluminescence (PL) quantum yield of 2% at room temperature (RT; 75 ± 5% at 77 K) and a fast PL lifetime of 18 ns at room temperature.
ISSN:0897-4756
1520-5002
DOI:10.1021/acs.chemmater.9b00038