Cadmium Dicyanoaurates and Their Reaction with Ammonia.

The synthesis and crystal structures of two anionic cadmium dicyanoaurate coordination polymers, [nBu4N]6[(Cd4Cl4)2(Au(CN)2)12][CdCl4] (TCCA) and [nBu4N]2[Cd(Au(CN)2)4], and their reaction with ammonia vapour is reported. TCCA and the isostructural [nBu4N]6[(Cd4Br4)2(Au(CN)2)12][CdBr4] form 3-D arrays with [Cd4X4]4+ (X=Cl, Br) cubane clusters linked from each octahedral Cd(II) centre by three bridging [Au(CN)2]- units. TCCA reacts with ammonia with concentrations of 1000 ppm or higher to give a product with a quantum yield of 0.88, while [nBu4N]2[Cd(Au(CN)2)4], which forms a 2-D anionic Cd[Au(CN)2]2 sheet structure with axially pendant [Au(CN)2]- units, reacts with concentrated ammonia vapour to generate Cd(NH3)2[Au(CN)2]2; this has a similar 2-D sheet structure but with axial NH3 units. Vibrational spectroscopy illustrated that the reaction of both Cd/[Au(CN)2]-based materials with ammonia proceeded by breaking Cd-NC bonds. For [nBu4N]2[Cd(Au(CN)2)4], this results in decomposition into [nBu4N][Au(CN)2] ⋅ 0.5H2O and Cd(NH3)2[Au(CN)2]2, while the reaction of ammonia with TCCA is reversible by heating the ammonia-bound sample above 110 °C. Cd[Au(CN)2]2 can be prepared by thermal removal of NH3 units from Cd(NH3)2[Au(CN)2]2.

Zinc Tetracyanoplatinate: A Reversible Luminescence-Based Ammonia Sensor.

ZnPt(CN)4 was shown to be an effective material for ammonia sensing, and can be synthesized using either solution or mechanochemical methods. A combination of luminescence and Raman spectroscopy revealed that multiple species are involved in the reaction between ammonia and ZnPt(CN)4 . The crystal structure of one of these species, Zn(NH3 )2 Zn(NH3 )3 (Pt(CN)4 )2 , was elucidated. Detection of ammonia vapor down to 50 ppm in air was accomplished by monitoring the luminescence spectrum. The reaction between ZnPt(CN)4 and ammonia vapor is reversible, and can be cycled multiple times by either flowing air over the material or heating. ZnPt(CN)4 also has a relatively high thermal stability, decomposing only when heated above 420 °C.