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

• Main Author: Nikolay Gerasimchuk
• Format: Article
• Language: English
• Published: MDPI AG 2011-09-01
• Series: Polymers
• Subjects: cyanoximes; coordination polymers of Tl(I) and Ag(I); X-ray analysis; UV-radiation; sensors
• Online Access: http://www.mdpi.com/2073-4360/3/3/1475/

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.