チオフェン置換ピロール合成ビルディングブロック

ピロールやチオフェンなどのヘテロ芳香環を基本骨格に含むπ共役系ポリマーは，センサーやエレクトロクロミック材料などへの応用が期待されています。Shimらは1,4-ジ(2-チエニル)-1,4-ブタンジオンを原料に用い，チオフェンを置換基に持つピロールモノマーを合成しています。in situ電解重合により電極に生成したポリマーフィルムは，電圧0.0 Vで黄色，1.0 Vで青色，応答速度0.95秒の良好なエレクトロクロミズムを示しています。

“Synthesis, electrochemical, and spectroelectrochemical properties of conductive poly-[2,5-di-(2-thienyl)-1H-pyrrole-1-(p-benzoic acid)]”

Y. H. Kim, J. Hwang, J. I. Son, Y.-B. Shim, Synth. Met. 2010, 160, 413. DOI: 10.1016/j.synthmet.2009.11.021

Poly(ter-heteroaromatic(thiophene–pyrrole–thiophene)), PDPB, was electrochemically prepared from the 2,5-di(2-thienyl)-1H-pyrrole-1-(p-benzoic acid) (DPB) monomer using the Paal-Knorr pyrrole condensation reaction. The structure of the monomer was confirmed using ¹H-, ¹³C NMR, FT-IR and mass spectroscopy. The maximum UV–visible absorption and PL emission bands of DPB were observed at 330 nm and 500 nm, respectively. The cyclic voltammograms (CVs) recorded for the electrochemically polymerized DPB revealed a set of redox peaks at 0.65/0.53 V. The conductivity monotonically increased with respect to the applied potential from 0.0 V to 1.0 V, exhibiting a maximum conductivity of 0.18 S/cm at +0.80 V. The in situ UV–visible spectroelectrochemical analysis of PDPB revealed electronic transitions at 420 nm, 654 nm, and 870 nm corresponding to the π–π* transition, polaron, and bipolaron states, respectively. The optical band-gap (E_g) of PDPB was 2.16 eV. The color of the PDPB film transitioned yellow (at 0.0 V) to blue (at 1.0 V) when the potential was switched between the reduced and oxidized states with a good electrochromic response time (0.95 s).