Facile surfactant-thermal syntheses and characterization of quaternary copper thioantimonates(III) ACu 2 SbS 3 (A = K, Rb, Cs)

Rb2CuSb7S12: Quaternary Antimony-Rich Semiconductor Featuring a Three-Dimensional Open Framework and Exhibiting an Intriguing Photocurrent Response

“…The experimental energy gap (E g ) of Rb 2 CuSb 7 S 12 is 1.54 eV, which is comparable to those of the previously reported Cubased thioantimonates. 5,6,10,11 From Figure 3c, it can be clearly observed that the highest valence band (VB) and lowest conduction band (CB) values for Rb 2 CuSb 7 S 12 are situated at the same F points. The calculated band structure indicates that Rb 2 CuSb 7 S 12 is a direct-band-gap semiconductor with a E g of 1.65 eV.…”

“…It is worth mentioning that the structure change trend of these compounds does not follow the previously reported inherent laws between the structural dimension and guest/host metal atom ratio. 17−21 For instance, RbCuSb 2 S 4 10 and KCu 2 SbS 3 11 show identical A/(Cu + Sb) ratios (i.e., 0.33), but the former possesses a 3D framework structure and the latter adopts a 2D-layered structure. Further structural analysis shows that the Cu/Sb ratio is the major determinant of structural dimension change (shown below).…”

“…In spite of the fact that a great number of Sb-based chalcogenides have been discovered over the last 10 years, quaternary A/Cu/Sb/Q (A = alkali metals; Q = chalcogen) compounds remain rare. So far, four types of structures are reported and given based on their different stoichiometries as follows: 1–1–2–4 type (i.e., RbCuSb 2 S 4 and CsCuSb 2 S 4 ), 1–2–1–3 type [i.e., ACu 2 SbS 3 (A = K, Rb, and Cs) and KCu 2 SbSe 3 ], 2–1–1–3 type (i.e., Na 2 CuSbS 3 and K 2 CuSbS 3 ), and 2–2–2–5 type (i.e., Rb 2 Cu 2 Sb 2 S 5 , Cs 2 Cu 2 Sb 2 S 5 , and Cs 2 Cu 2 Sb 2 Se 5 ). It is worth mentioning that the structure change trend of these compounds does not follow the previously reported inherent laws between the structural dimension and guest/host metal atom ratio. − For instance, RbCuSb 2 S 4 and KCu 2 SbS 3 show identical A/(Cu + Sb) ratios (i.e., 0.33), but the former possesses a 3D framework structure and the latter adopts a 2D-layered structure.…”

Facile Hydrazine‐Hydrothermal Syntheses and Characterizations of Two Quaternary Thioarsenates(III): Two‐Dimensional SrAg4As2S6⋅2 H2O and One‐Dimensional BaAgAsS3

“…Thiometallates containing group 15 elements have attracted increasing attention of researchers owing to their structural diversity and potential applications such as in nonlinear optics, ion exchange, and photocatalysis . Thioarsenates(III), a subclass of thiometallates, exhibit a special structural feature of the stereochemically active lone electron pairs, which is distinctly different from that of all other thiometallates .…”

Effect of alkali cations on two-dimensional networks of two new quaternary thioarsenates (III) prepared by a facile surfactant-thermal method

“…acidic, basic, neutral, cationic, anionic, or even block), surfactants, as the efficient reaction media, have been successfully used to prepare novel chalcogenides by Zhang group [33][34][35][36]. Recently, the use of surfactants for preparing inorganic quaternary chalcogenides has been further developed by our group [37,38]. To continue on this strategy, two new quaternary thioarsenates(III) NaAg 2 AsS 3 Á H 2 O (1) and KAg 2 AsS 3 (2) with interesting two-dimensional (2D) layer structures were successfully synthesized.…”