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• Six thioarsenates and thioantimonates with different valences of As/Sb were synthesized by adjusting the temperature. • Cs 2 Ag 6 As 2 S 7 (5) exhibits the highest Ag/As ratio among the known quaternary sulfides. • Compounds 4 and 5 exhibit excellent photoelectric responsive properties. [Display omitted] Six thioarsenates and thioantimonates with different valences of As/Sb were synthesized solvothermally by adjusting the synthetic temperature. Rb 2 AgAsS 4 (1), Cs 2 AgAsS 4 (2), Cs 2 AgSbS 4 (3) in which As and Sb are pentavalent were obtained in the lower temperature system and RbAg 2 AsS 3 (4), Cs 2 Ag 6 As 2 S 7 (5), and CsAg 2 SbS 3 (6) in which As and Sb are trivalent were synthesized under a higher temperature. Compounds 1 – 3 possess the same one-dimensional (1D) chain structure and 4 – 6 are two-dimensional (2D) layered compounds. In particular, 5 exhibits the highest Ag/As ratio (3.0) among the known quaternary sulfides, and rare octahedral coordinated S2- ions that coordinate with six Ag+ ions exist in the structure of it. Their optical properties, photoelectric response properties, and theoretical calculations have also been studied. [ABSTRACT FROM AUTHOR]

Four layered quaternary sulfides KAgCdS 2 (1), RbAgCdS 2 (2), CsAgCdS 2 (3), and Cs 2 Cu 2 Cd 2 S 4 (4) have been successfully synthesized by mild solvothermal methods by employing excess sulfur as a mineralizer. Compound 1 possesses anionic [AgCdS 2 ] n n− double layers. Compounds 2 and 3 are isostructural and contain anionic [AgCdS 2 ] n n− single layers. Although both of the two structures are constructed by edge-sharing [MS 4 ] (M = Ag/Cd) tetrahedral units, their condensation behaviors are totally different. The structure of 4 consists of infinite [Cd 2 S 4 ] n 4n− chains and [CuS 2 ]2- dumbbells that linked to form [Cu 2 Cd 2 S 4 ] n 2n− layers. According to the UV–vis diffuse reflectance experiments, the band gaps of the title compounds are 1.92 eV (1), 2.16 eV (2), 2.42 eV (3), and 2.23 eV (4). Additionally, the photoelectrochemical experiments indicate that compounds 2 and 3 exhibit excellent photocurrent responsive properties. Image 1 • Compounds KAgCdS 2 (1), RbAgCdS 2 (2), CsAgCdS 2 (3), and Cs 2 Cu 2 Cd 2 S 4 (4) were synthesized by solvothermal methods. • Excess sulfur was firstly extended to the mineralizing of quaternary sulfides containing two late transition metals. • Compounds RbAgCdS 2 (2) and CsAgCdS 2 (3) exhibit excellent photocurrent responsive properties. [ABSTRACT FROM AUTHOR]

Two compounds Ba 2 Cu 2 Cd 2 S 5 (1) and Ba 3 Cu 4 Hg 4 S 9 (2) have been successfully synthesized under mild solvothermal conditions by using thiophenol as a mineralizer. Compound 1 features an anionic [Cu 2 Cd 2 S 5 ] n 4n− layer constructed by trigonal planar CuS 3 and tetrahedral CdS 4. Compound 2 possesses a unique [Cu 4 Hg 4 S 9 ] n 6n− layer composed of trigonal planar CuS 3 and linear HgS 2. Rare linear-coordinated sulfur and square-planar tetra-coordinated sulfur exist in the structures of 1 and 2 , respectively. In addition, the thermal stabilities, optical properties, photoelectric responses, as well as the band gap calculations of the two compounds were also studied in detail. Image 1 • Two layered sulfides Ba 2 Cu 2 Cd 2 S 5 (1) and Ba 3 Cu 4 Hg 4 S 9 (2) were synthesized by solvothermal method. • Thiophenol (PhSH) was used as an effective mineralizer in the mild method. • Unusual linear-coordinated and square-planar tetra-coordinated sulfur exist in compounds 1 and 2 , respectively. • Ba 2 Cu 2 Cd 2 S 5 (1) exhibits excellent photocurrent responsive property. [ABSTRACT FROM AUTHOR]

Four quaternary silver sulfides, Ba 2 AgInS 4 (1), Ba 3 Ag 2 Sn 2 S 8 (2), BaAg 2 MS 4 (M = Sn for 3 ; Ge for 4) have been synthesized solvothermally in the presence of excess sulfur as mineralizer. Compound 1 features a 2-D [ AgInS 4 ] 4 − ∞ 2 layer structure composed of AgS 4 /InS 4 tetrahedra, in which the two metals randomly occupy one crystallographic unique position with the molar ratio of 1:1. Compound 2 possesses a 3-D [Ag 2 Sn 2 S 8 ]6- framework which constructed by alternative arrangements between AgS 4 and SnS 4 tetrahedra by sharing vertexes. The structures of compounds 3 and 4 are similar and exhibit 3-D anionic [Ag 2 MS 4 ]2- (M = Sn for 3 ; Ge for 4) framework composed of AgS 2 layers and monomeric MS 4 (M = Sn, Ge) tetrahedra that pillar the above layers. Moreover, semiconducting properties (optical bandgap, photoelectric response) of the title compounds were also investigated. The results indicate that all the quaternary sulfides are narrow-gap semiconductors, and compound 3 exhibits excellent photocurrent responsive property. Image 1 • Four quaternary alkaline earth metal silver sulfides were synthesized by solvothermal method. • Excess sulfur was used as an effective mineralizer in the mild method. • Compound Ba 3 Ag 2 Sn 2 S 8 (2) feature a unique 3-D framework constructed by isolated AgS 4 and SnS 4 tetrahedra. • Compound BaAg 2 SnS 4 (3) exhibits excellent photocurrent responsive property. [ABSTRACT FROM AUTHOR]