Kinetics of Excimer Electrogenerated Chemiluminescence of Pyrene and 1-Pyrenebutyricacid 2-Ethylhexylester in Acetonitrile and an Ionic Liquid, Triethylpentylphosphonium Bis(trifluoromethanesulfonyl)imide

Ryoichi Ishimatsu*, Shuya Tashiro, Takashi Kasahara, Juro Oshima, Jun Mizuno, Koji Nakano, Chihaya Adachi, Toshihiko Imato

*この研究の対応する著者

研究成果査読

1 被引用数 (Scopus)

抄録

We describe the kinetics of excimer electrogenerated chemiluminescence (ECL) of a liquid pyrene derivative, 1-pyrenebutyricacid 2-ethylhexylester (PLQ) dissolved in a molecular solvent, acetonitrile (MeCN), and an ionic liquid, triethylpentylphosphonium bis(trifluoromethanesulfonyl)imide ([P2225][TFSI]). Pyrene was also used for comparison. To discuss the kinetics of the excimer ECLs, the photophysical and electrochemical properties and electronic states of PLQ and pyrene were revealed. The photoluminescence (PL) spectra, rate constants for the radiative transitions, and redox potentials of PLQ and pyrene dissolved in MeCN and [P2225][TFSI] suggest that as a solvent, [P2225][TFSI] behaves more polar than MeCN. By analyzing the PL decay curves, the rate constants to form the excimer were determined to be on the order of 109 and 107 M-1 s-1 in MeCN and [P2225][TFSI], respectively, which were limited by the diffusion. For neat PLQ (1.6 M), a delay of 0.3-0.4 ns for the excimer emission compared to the monomer emission was observed. It is likely that the delay corresponds to the timescale for arranging the conformation to form the excimer. The ECL of PLQ was generated by applying a square wave voltage to produce the radical anion and cation, and on the ECL spectra, the excimer emission was more prevailed compared to the PL spectra. Kinetic analysis for the electron transfer reaction between the radical ions based on Marcus theory indicates that the electron transfer is limited by the diffusion of the radical ions. Moreover, the electron transfer distance (det) between the radical cation and anion to generate excited states was calculated with a framework of the theory. Kinetically, the electron transfer can take place at det < 11 Å in MeCN and det < 12 Å in [P2225][TFSI]. The density functional theory (DFT) and time-dependent DFT calculations show that the potential energy curve of the excimer against the distance between the pyrene rings reaches a minimum at 3.50 Å. This suggests that through the electron transfer, the process of the direct formation of the monomer S1 state followed by the excimer formation is more prevailed than that of the direct excimer formation.

本文言語English
ページ(範囲)10825-10836
ページ数12
ジャーナルJournal of Physical Chemistry B
123
50
DOI
出版ステータスPublished - 2019 12 19

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 表面、皮膜および薄膜
  • 材料化学

フィンガープリント

「Kinetics of Excimer Electrogenerated Chemiluminescence of Pyrene and 1-Pyrenebutyricacid 2-Ethylhexylester in Acetonitrile and an Ionic Liquid, Triethylpentylphosphonium Bis(trifluoromethanesulfonyl)imide」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル