Kinetics of Excimer Electrogenerated Chemiluminescence of Pyrene and 1-Pyrenebutyricacid 2-Ethylhexylester in Acetonitrile and an Ionic Liquid, Triethylpentylphosphonium Bis(trifluoromethanesulfonyl)imide
| Autor: | Ryoichi Ishimatsu, Shuya Tashiro, Koji Nakano, Toshihiko Imato, Juro Oshima, Chihaya Adachi, Takashi Kasahara, Jun Mizuno |
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| Rok vydání: | 2019 |
| Předmět: |
Materials science
010304 chemical physics 010402 general chemistry Excimer Photochemistry 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Marcus theory chemistry.chemical_compound Electron transfer chemistry Radical ion Excited state 0103 physical sciences Ionic liquid Materials Chemistry Pyrene Physical and Theoretical Chemistry Acetonitrile |
| Zdroj: | The Journal of Physical Chemistry B. 123:10825-10836 |
| ISSN: | 1520-5207 1520-6106 |
| Popis: | 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 A in MeCN and det < ∼12 A 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 A. 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. |
| Databáze: | OpenAIRE |
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