Cu₉Bi₉S₁₆Cl₈ und Cu_7.4Bi₆Se₁₂Cl₇ – Polyedernetzwerke mit Dichalkogenidbrücken und mobilen Kupfer(I)‐Kationen

Abstract

Abstract. Melting reactions of Cu, CuCl, Q (Q = S, Se), and Bi 2 Q 3 yield black, shiny needles of the

The Low‐Valent Bismuth Sulfide Bromide Cu3Bi2S3Br2

“…On the other hand, oxidized species that include dichalcogenide dumbbells, e.g. Cu 9 Bi 9 S 16 Cl 8 12 or Cu 4– δ BiSe 4 I,13 demonstrate further options for redox chemistry in this class of quaternary compounds.…”

Cu7Bi6S10Cl5 – Mobile Copper(I) Cations Inside Dendritic Channels of a Rigid Framework

“…Each of the three independent bismuth cations is coordinated by three sulfur and four chlorine anions in the shape of a mono‐capped trigonal prism. Such coordination spheres of anions surrounding bismuth cations are already reported for substances like Cu 3 Bi 2 S 4 Cl 5 or Cu 9 Bi 9 S 16 Cl 8 7. The [BiS 3 Cl 4 ] polyhedra share edges and faces resulting in compact rods with six prisms in the cross section running along [010] and eventually in corrugated layers $\rm ^2_\infty[Bi_6S_{10}Cl_5]^{7-}$ parallel ($\bar2$ 01).…”

“…For example, Cu 3 Bi 2 S 4 Cl 5 or Cu 3 Bi 2 S 3 I 3 6 are considered to be mixed conductors, where the different phenomena are not unidirectional. Our aim was to reveal a greater range to such highly anisotropic materials, as already successful reported in previous work 7. Here, we present a new quaternary compound in the system Cu/Bi/S/Cl, which exhibits a rigid bismuth‐anion network and inherent disordered Cu I cations.…”

“…Consequently the chemical surrounding of the copper cations is dominated by sulfur anions. The feature that the mobile copper ions are coordinated by the more polarizable anions is known from related compounds like Cu 9 Bi 9 S 16 Cl 8 7 as well.…”

Copper Bismuth Chalcogenide Halogenides with Extensively Disordered and Mobile Copper(I) Cations

“…Mixed Cu/Bi occupancy in networksof octahedra was also found in the minerals hodrushite(Cu 8 Bi 12 S 22 )7 and cuprobismutite (Cu 10 Bi 12 S 23 ),8 as well as in synthetic compounds such as Cu 9 BiS 6 ,9 the pavonitehomologues Cu 1.77 Bi 4.57 S 8 10 and Cu 2.93 Bi 4.79 S 9 ,11 andCu 1.57 Bi 2.37 Se 2.68 Br 3.32 4g. On the other hand, there are numerous related compounds, predominantly chalcogenide halogenides, with various structure types, in which copper does not occupy the bismuth sites, such as CuBiSCl 2 ,4cCu 9 Bi 9 S 16 Cl 8 ,4e Cu 7.4 Bi 6 Se 12 Cl 7 ,4e Cu 7 Bi 6 S 10 Cl 5 ,4fCu 22 Bi 12 S 21 Cl 16 ,4h Cu 3 BiS 2 Br 2 ,4i and Cu 4 Bi 3 S 5 Br 1.81 Cl 1.19 4i…”