Abstract
We report the first examples of thiocyanate-based analogues of the cyanide Prussian blue compounds, MIII[Bi(SCN)6], M = Fe, Cr, Sc. These compounds adopt the primitive cubic pcu topology and show strict cation order. Optical absorption measurements show these compounds have band gaps within the visible and near IR region, suggesting that they may be useful for applications where light harvesting is key, such as photocatalysis. We also show that Cr[Bi(SCN)6] can reversibly uptake water into its framework structure pointing towards the possibility of using these frameworks for host/guest chemistry.
Highlights
Synthesis of HSCNIn a 250 mL round bottom ask, NH4SCN (5 g, 65.7 mmol) was dissolved in 5 mL H2O and cooled to 0 C in an ice bath
All publication charges for this article have been paid for by the Royal Society of Chemistry
All three compounds were synthesised by reacting thiocyanatobismuthate solutions, in dilute nitric acid or polar aprotic solvents, with a transition metal source
Summary
In a 250 mL round bottom ask, NH4SCN (5 g, 65.7 mmol) was dissolved in 5 mL H2O and cooled to 0 C in an ice bath. Excess Fe2O3 was ltered off under vacuum, and the deep red solution was le to slowly evaporate over a few days, yielding diffraction quality very dark green single crystals of Fe [Bi(SCN)6]. The reaction mixture was stirred for overnight and ltered to remove KNO3, yielding a very deep purple solution of Fe[Bi(SCN)6]. This solution was evaporated to dryness, and extracted using 100 mL of dry tetrahydrofuran. The reaction mixture was stirred for overnight and ltered to remove KNO3, yielding an orange solution of Sc[Bi(SCN)6]. This solution was evaporated to dryness from which diffraction quality single crystals of Sc[Bi(SCN)6] could be obtained. Cr[Bi(SCN)6]$H2O is formed when this synthesis is carried out using 3 N HNO3 as a solvent for (NH4)3[Cr(NCS)6] and when Cr[Bi(SCN)6] is exposed to ambient humidity over a period of weeks
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