Copper(I) thiocyanate (or cuprous thiocyanate) is a coordination polymer with formula CuSCN. It is an air-stable, white solid used as a precursor for the preparation of other thiocyanate salts.

Structure

At least two polymorphs have been characterized by X-ray crystallography. They both feature copper(I) in a characteristic tetrahedral coordination geometry. The sulfur end of the SCN- ligand is triply bridging so that the coordination sphere for copper is CuS3N.Smith, D. L.; Saunders, V. I. "Preparation and Structure Refinement of the 2H Polytype of beta-Copper(I) Thiocyanate" Acta Crystallographica B, 1982, volume 38, 907-909.

Synthesis

Copper(I) thiocyanate forms from the spontaneous decomposition of black copper(II) thiocyanate, releasing thiocyanogen, especially when heated. It is also formed from copper(II) thiocyanate under water, releasing (among others) thiocyanic acid and the highly poisonous

hydrogen cyanide Hydrogen cyanide (formerly known as prussic acid) is a chemical compound with the chemical formula, formula HCN and structural formula . It is a highly toxic and flammable liquid that boiling, boils slightly above room temperature, at . HCN is ...

. It is conveniently prepared from relatively dilute solutions of copper(II) in water, such as copper(II) sulphate. To a copper(II) solution sulphurous acid is added and then a soluble thiocyanate is added (preferably slowly, while stirring). Copper(I) thiocyanate is precipitated as a white powder. Alternatively, a

thiosulfate Thiosulfate ( IUPAC-recommended spelling; sometimes thiosulphate in British English) is an oxyanion of sulfur with the chemical formula . Thiosulfate also refers to the compounds containing this anion, which are the salts of thiosulfuric acid, ...

solution may be used as a reducing agent.

Double salts

Copper(I) thiocyanate forms one double salt with the group 1 elements, CsCu(SCN)₂. The double salt only forms from concentrated solutions of CsSCN, into which CuSCN dissolves. From less concentrated solutions, solid CuSCN separates reflecting its low solubility. When brought together with potassium,

sodium Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...

or barium thiocyanate, and brought to crystallisation by concentrating the solution, mixed salts will crystallise out. These are not considered true double salts. As with CsCu (SNC)₂, copper(I) thiocyanate separates out when these mixed salts are redissolved or their solutions diluted.

Uses

Copper(I) thiocyanate is a

hole A hole is an opening in or through a particular medium, usually a solid Body (physics), body. Holes occur through natural and artificial processes, and may be useful for various purposes, or may represent a problem needing to be addressed in m ...

conductor, a

semiconductor A semiconductor is a material with electrical conductivity between that of a conductor and an insulator. Its conductivity can be modified by adding impurities (" doping") to its crystal structure. When two regions with different doping level ...

with a wide band gap (3.6 eV, therefore transparent to visible and near infrared light). It is used in photovoltaics in some third-generation cells as a hole transfer layer. It acts as a P-type semiconductor and as a

solid-state electrolyte A solid-state electrolyte (SSE) is a solid Ionic conductivity (solid state), ionic conductor and electron-insulating electrolyte, material and it is the characteristic component of the solid-state battery. It is useful for applications in electric ...

. It is often used in dye-sensitized solar cells. Its hole conductivity is however relatively poor (0.01 S·m⁻¹). This can be improved by various treatments, e.g. exposure to gaseous

chlorine Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...

or doping with (SCN)₂. CuSCN with NiO act synergically as a smoke suppressant additive in polyvinyl chloride (PVC). CuSCN precipitated on carbon support can be used for conversion of aryl halides to aryl thiocyanates. Copper thiocyanate is used in some anti-fouling paints. Advantages compared to cuprous oxide include that the compound is white and a more efficient biocide.

References

{{DEFAULTSORT:Copper(I) thiocyanate Copper(I) compounds Thiocyanates Semiconductor materials Coordination polymers