Synthesis and electronic properties of N-heterocyclic carbene-containing conducting polymers with coinage metals

Abstract

The recent development of functional materials based on conducting metal-containing polymer, we designed and synthesized a series of bithiophene based N-heterocyclic carbene (NHC)-conducting polymer using coinage metals (Cu, Ag, and Au). Absorption spectroscopy, NMR spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy (XPS) were used to analyze the monomers and polymer thin films. The peak current of the electrodeposited film on the Ptbutton electrodes increased proportionally with a scan rate exhibited the stability of polymer thin films. Remarkably, in the electrochemical studies of the coinage metals complexes, the redox potential of the Cu + /Cu 2+ perfectly matched with quaterthiophene moieties of the polymer backbone redox wave. However, the redox potential of Ag/Ag + did not matched with the redox potential of the polymer backbone. During the oxidation process in the spectroelectrochemical studies, conducting coinage metallopolymers exhibited a drastic color change from orange (reduced form) to dark green (oxidized form) and can be envisioned in the application of electrochromic materials.

N‐Heterocyclic Carbene‐Protected Ag Nanoparticles Immobilized on Polyacrylonitrile Fiber as Efficient Catalysts for a Three‐Component Coupling Reaction

“…In addition, the high‐resolution XPS spectrum (Figure b) shows the typical doublet (resulting from spin‐orbital splitting) for an electron on a 3d level of Ag. Furthermore, the high‐resolution Ag XPS spectrum of PANF‐NHC‐Ag contained two peaks at 368.35 and 374.28 eV (Figure b‐I), which corresponded to Ag 3d 3/2 and 3d 5/2 , respectively, and which can be attributed to the NHC‐Ag complex . Following reduction, the high‐resolution Ag XPS spectrum of PANF‐NHC@Ag contained two peaks at 368.03 and 374.02 eV (Figure b‐II), which corresponded to Ag 3d 3/2 and 3d 5/2 , respectively, and were attributed to the Ag nanoparticles .…”

“…35 and 374.28eV ( Figure 6b-I), which corresponded to Ag 3d 3/2 and 3d 5/2 ,r espectively,a nd which can be attributed to the NHC-Ag complex. [33] Followingr eduction, the high-resolution Ag XPS spectrum of PANF-NHC@Ag contained two peaks at 368.03 and 374.02eV ( Figure 6b-II), whichc orresponded to Ag 3d 3/2 and 3d 5/2 ,r espectively,a nd were attributed to the Ag nanoparticles. [31] The Ag 3d peak for the recycled supported NPs is also shown (Figure 6b-III), which demonstrates that Ag 0 was the dominant form of Ag following catalystrecycling.…”

Polyacrylonitrile Fiber Supported N-Heterocyclic Carbene Ag(I) As Efficient Catalysts for Three-Component Coupling and Intramolecular 1,3-Dipolar Cycloaddition Reactions under Flow Conditions

“…The high resolution Ag 3d spectrum of PANF-NHC-Ag (Figure 1b) can be deconvoluted into two groups' peaks which correspond to Ag(I) (374.28 and 368.25 eV) and Ag(0) (372.98 and 367.02 eV; oxidation states of Ag, see Supporting Information Table S1). 53,54 Solid-state 13 C NMR (Figure 2) was also used to characterize the modified fibers. The pure PANF has the following characteristic peaks: the backbone carbon peak is at around 29.7 ppm; the cyano carbon peak is centered at 122.1 ppm, and the ester carbonyl carbon peak is at 174.5 ppm.…”

“…The full survey spectrum of 4b (Figure a) shows principal energy levels for O 1s, N 1s, Ag 3d, C 1s, and Cl 2p at 536.20, 403.76, 370.19, 376.17, 287.41, and 200.96 eV. The high resolution Ag 3d spectrum of PANF-NHC-Ag (Figure b) can be deconvoluted into two groups’ peaks which correspond to Ag­(I) (374.28 and 368.25 eV) and Ag(0) (372.98 and 367.02 eV; oxidation states of Ag, see Supporting Information Table S1). , …”

N-Heterocyclic Carbenes in Materials Chemistry

“…Electrochemical polymerization techniques have also been used to access polymeric NHC–metal complexes. − In this context, Cowley and co-workers employed an electropolymerization method to synthesize polymeric NHC–metal complexes ( 225 , Figure ). For this purpose, they prepared an NHC–Ag monomer bearing two bithiophene groups in the backbone, which was then electropolymerized onto a platinum disk or an indium tin oxide glass slide.…”