An Excursion into the Intriguing World of Polymeric Tl(I) and Ag(I) Cyanoximates^†

Abstract: The reaction of hot (~95 °C) aqueous solutions of Tl₂CO₃ with solid HL (HL = NC-C(=N-OH)-R is a cyanoxime, and R is an electron-withdrawing group; 37 ligands are known up-to-date) leads to crystalline yellow/orange TlL. Similarly, the reaction between AgNO₃ and ML (M = K⁺, Na⁺; L = anion of the monodeprotonated cyanoxime) this time at room temperature in mixed ethanol/aqueous solutions leads to sparingly soluble, colored AgL in high-yield. All synthesized monovalent Tl and Ag complexes were characterized using a variety of spectroscopic methods and X-ray analysis, which revealed the formation of primarily 2D coordination polymers of different complexity. In all cases cyanoxime mono-anions act as bridging ligands. Thallium(I) cyanoximates adopt in most cases a double-stranded motif that is originated from centrosymmetric (TlL)₂ dimers in which two Tl₂O₂ rhombs are fused into infinite “ladder-type” structure. There are very short (3.65–3.85 Å) intermetallic distances in (TlL)_n, which are close to that (3.46 Å) in metallic thallium. This opens the possibility for the electrochemical or chemical generation of mixed valence Tl(I)/Tl(III) polymers that may exhibit electrical conductivity. Synthesized silver(I) compounds demonstrate a very significant (for multiple years!) stability towards visible light. There are three areas of potential practical applications of these unusual complexes: (1) battery-less detectors of UV-radiation, (2) non electrical sensors for gases of industrial importance, (3) antimicrobial additives to light-curable acrylate polymeric glues, fillers and adhesives used during introduction of indwelling medical devices. Chemical, structural, technological and biological aspects of application of Tl(I) and Ag(I) cyanoximes-based coordination polymers are reviewed.