Semiconductive K2MSbS3(SH) (M = Zn, Cd) Featuring One-Dimensional ∞1[M2Sb2S6(SH2)]4- Chains

Xian Zhang; Na Yi; Roald Hoffmann; Chong Zheng; Jianhua Lin; Fuqiang Huang

doi:10.1021/acs.inorgchem.6b01529

Semiconductive K₂MSbS₃(SH) (M = Zn, Cd) Featuring One-Dimensional _∞¹[M₂Sb₂S₆(SH₂)]^4- Chains

Inorg Chem. 2016 Oct 3;55(19):9742-9747. doi: 10.1021/acs.inorgchem.6b01529. Epub 2016 Sep 15.

Authors

Xian Zhang¹, Na Yi², Roald Hoffmann³, Chong Zheng⁴, Jianhua Lin¹, Fuqiang Huang^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, P. R. China.
² State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences , Shanghai 200050, P. R. China.
³ Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
⁴ Department of Chemistry and Biochemistry, Northern Illinois University , DeKalb, Illinois 60115, United States.

PMID: 27628522
DOI: 10.1021/acs.inorgchem.6b01529

Abstract

We synthesized two one-dimensional compounds K₂MSbS₃(SH) (M = Zn, Cd) at 473 K, using thiourea as reactive flux. The compounds crystallize in the triclinic space group P1̅. Their structures feature one-dimensional _∞¹[M₂Sb₂S₆(SH₂)]^4- double chains along the crystallographic a axis. The _∞¹[M₂Sb₂S₆(SH₂)]^4- double chains are composed of [M₂Sb₂S₈(SH)₂]^8- eight-membered rings. Similar band gaps of the two compounds, E_g = 2.75 eV for K₂ZnSbS₃(SH) and E_g = 2.71 eV for K₂CdSbS₃(SH), were obtained from optical absorption measurements, which are consistent with theoretical calculations. The analysis of density of states indicates that the valence band maximum and conduction band minimum consist mainly of S-3p orbitals and Sb-5p orbitals, respectively.