Application of terpyridyl ligands to tune the optical and electrochemical properties of a conducting polymer

Abstract

We present a simple and effective way of using metal and metal–ligand modifications to tune the electrochemical and optical properties of conducting polymers.

Polyterthiophenes Cross‐Linked with Terpyridyl Metal Complexes for Molecular Architecture of Optically and Electrochemically Tunable Materials

“…The spectrum recorded with 457 nm laser line ( Figure 2B) exhibits features similar to doped polythiophene, and is alike previously obtained for poly(TTPy) films. [26,42] At the 594 nm excitation, however, the spectral pattern in 1500-1440 cm À 1 range is clearly influenced by MLCT transitions, as compared with the reference modes for Fe(TPy) 2 observed at 1498 and 1473 cm À 1 (Figure 2A), and with an obtained absorption maximum of 596 nm for dπ-π* transitions, Figure 1B. This finding supports the proposed hypothetical structure of poly(Fe[(TTPy) 2 ] 2 + ) film shown in Figure 1A.…”

“…[25] To form poly(TTPy) films, a 5 mM concentration monomer solution was obtained by dissolving it in 0.1 M TBAP in 1 : 1 ACN:DCM and the solution subject to cyclic voltammetry (CV) using an eDAQ system controlled by EChem software as previously reported. [26] In the three-electrode system utilized, indium tin oxide (ITO) glass slides (1.55 cm 2 ) were used as the working electrode (WE), Ag/Ag + (0.1 M TBAP + ACN, E Fc/Fc + = 0.09 V) as the reference electrode (RE), and Pt mesh as the counter electrode (CE). The electrochemical synthesis was done by performing one potential cycle between À 0.2 and 0.8 V with 0.1 V s À 1 scan rate.…”

“…The terpyridines are metal complexing ligands, forming stable 2 : 1 complexes with various metal ions. [23][24][25][26] The stable ligand-metal interactions allow the building of complex structures, based on e. g. polymers with ligand moieties in the polymer backbone or in the side chain. [27][28][29][30][31][32][33] For instance, by introducing and further exchanging different metals in a polythiophene bearing terpyr-idine (TPy) functionality, various optical and electrochemical properties were obtained.…”

“…[27][28][29][30][31][32][33] For instance, by introducing and further exchanging different metals in a polythiophene bearing terpyr-idine (TPy) functionality, various optical and electrochemical properties were obtained. [26] Thus, such functionalizations led to the development of tunable materials by relatively simple metallo-organic complexes molecular architecture. [26,34,35] In this work macromolecular iron(II) complex with (E)-4'-(2-(4,4"-bisdecyloxy-2,2':5',2"-terthiophene-3'yl)ethenyl)-2,2':6',2"terpyridine (TTPy) ligand (Fe[(TTPy) 2 ] 2 + ) was used to obtain poly (Fe[(TTPy) 2 ] 2 + ) as a novel functional material.…”

“…[26] Thus, such functionalizations led to the development of tunable materials by relatively simple metallo-organic complexes molecular architecture. [26,34,35] In this work macromolecular iron(II) complex with (E)-4'-(2-(4,4"-bisdecyloxy-2,2':5',2"-terthiophene-3'yl)ethenyl)-2,2':6',2"terpyridine (TTPy) ligand (Fe[(TTPy) 2 ] 2 + ) was used to obtain poly (Fe[(TTPy) 2 ] 2 + ) as a novel functional material. The presence of Fe 2 + cations during electrochemical synthesis provides a facile approach for cross-linking poly(TTPy) macromolecules (Figure 1 A).…”