Organic-Inorganic Hybrid Tin Halide Single Crystals with Sulfhydryl and Hydroxyl Groups: Formation, Optical Properties, and Stability

Zhexin Song; Binyin Yu; Jing Wei; Chunlong Li; Guokui Liu; Yangyang Dang

doi:10.1021/acs.inorgchem.2c00313

Organic-Inorganic Hybrid Tin Halide Single Crystals with Sulfhydryl and Hydroxyl Groups: Formation, Optical Properties, and Stability

Inorg Chem. 2022 May 9;61(18):6943-6952. doi: 10.1021/acs.inorgchem.2c00313. Epub 2022 Apr 29.

Authors

Zhexin Song¹, Binyin Yu¹, Jing Wei², Chunlong Li³, Guokui Liu⁴, Yangyang Dang^{1

5}

Affiliations

¹ Shandong Provincial Key Laboratory of Laser Polarization and Information Technology, School of Physics and Physical Engineering, Qufu Normal University, No. 57, Jingxuan West Road, Qufu 273165, P. R. China.
² Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications, Experimental Center of Advanced Materials School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, P. R. China.
³ State Key Laboratory of Biobased Material and Green Papermaking, Qilu University of Technology, Shandong Academy of Sciences, Jinan 250353, P. R. China.
⁴ School of Chemistry and Chemical Engineering, Linyi University, Linyi 276000, P. R. China.
⁵ Department of Chemistry, School of Sciences, and Collaborative Innovation Centre of Chemical Science and Engineering, Tianjin University, Tianjin 300072, P. R. China.

PMID: 35485722
DOI: 10.1021/acs.inorgchem.2c00313

Abstract

Lead (Pb)-free halide hybrid materials have received a great deal of attention because of their potential in optoelectronic applications. However, heteroatom-based amine lead-free tin halide hybrid single crystals have not been well investigated yet. Detailed synthetic processes, growth, crystal structures, and stability of (ACH₂CH₂NH₃)₂SnBr₆ (A = OH or SH) and (BCH₂CH₂NH₃)₂SnI₄ (B = I or SH) single crystals were investigated. Interestingly, (IH₃NCH₂CH₂SSCH₂CH₂NH₃)₂HPO₃ exhibited orange-red photoluminescence (PL) at about 620 nm with an average PL lifetime of about 912 ns. (HSCH₂CH₂NH₃)₂SnI₄ single crystals exhibited a PL peak at 620 nm with an average PL lifetime of about 0.607 ns. More importantly, (HSCH₂CH₂NH₃)₂SnI₄ single crystals exhibited reversible red-black color transformations when exposed to a H₃PO₂ solution and an ambient atmosphere, which was attributed to oxidation from Sn²⁺ to Sn⁴⁺, rather than from I^- to I₃^- (I₂). The intriguing characteristics should provide guidance for further optoelectronic applications of these Pb-free halide hybrid materials.