Coordination polymers incorporating gold(I) and platinum(II) cyanometallate linkers – chemical vapour sensors and beyond

This thesis focuses on the use of heterobimetallic coordination polymers incorporating dicyanoaurate and tetracyanoplatinate linkers as photoluminescence based vapour sensors for S-donors and ammonia. Other applications include the use of these materials as nonlinear optical media and conductive solids. Cu2/3Au1/3CN was shown to exhibit a rapid, reversible luminescent response to thioether vapours. Exposing HgPt(CN)4 to some thiol vapours resulted in drastic changes to their luminescence. CuI(Bz2S2) (Bz=benzyl) and CuI(Me2S2) were synthesized and structurally characterized. ZnPt(CN)4 was shown to reversibly react with ammonia to form Zn(NH3)2.5Pt(CN)4 with an accompanying change in luminescence. Raman spectroscopy was also used to detect ammonia via the νCN bands of Zn[Au(CN)2]2 and ZnPt(CN)4. The structure of [NBu4]6(Cd4Cl4)2(Au(CN)2)12[CdCl4] was determined and it was shown to be a turn-on ammonia sensor. A series of isostructural 1D coordination polymers, [PPN]MX2Au(CN)2 (M=Zn,Cd,Hg; X=Cl,Br,I), were shown to exhibit second harmonic generation. A potentially conductive coordination polymer [TTF]CdCl2Au(CN)2 was synthesized.