title: Synthesis and redox activity of "clicked" triazolylbiferrocenyl polymers, network encapsulation of gold and silver nanoparticles and anion sensing.
abstract: The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.
authors: ISM, UMR CNRS No. 5255, Université de Bordeaux, 33405 Talence Cedex, France.
authors: Amalia
authors: A
authors: Rapakousiou
authors: Christophe
authors: C
authors: Deraedt
authors: Joseba
authors: J
authors: Irigoyen
authors: Yanlan
authors: Y
authors: Wang
authors: Noël
authors: N
authors: Pinaud
authors: Lionel
authors: L
authors: Salmon
authors: Jaime
authors: J
authors: Ruiz
authors: Sergio
authors: S
authors: Moya
authors: Didier
authors: D
authors: Astruc
mesh_terms: D000838:Anions / Q000737:chemistry; D057930:Click Chemistry; D005296:Ferrous Compounds / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D053768:Metal Nanoparticles / Q000737:chemistry*; D000075163:Metallocenes; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010316:Particle Size; D011108:Polymers / Q000737:chemistry*; D012834:Silver / Q000737:chemistry; D013499:Surface Properties; D014230:Triazoles / Q000737:chemistry*
chemical_list: D000838:Anions; D005296:Ferrous Compounds; D000075163:Metallocenes; D009942:Organometallic Compounds; D011108:Polymers; D014230:Triazoles; D012834:Silver; D006046:Gold; C004998:ferrocene