Monomer and Excimer Emission in Electrogenerated Chemiluminescence of Pyrene and 2,7-Di-tert-butylpyrene Associated with Electron Transfer Distance.

Electrogenerated chemiluminescence (ECL) is a light emission phenomenon caused by electrochemically generated radical anions (R•-) and cations (R•+), in which the ion annihilation results in the formation of a pair of excited (R*) and ground state (R) of a luminescent molecule. Here, the ECL properties of pyrene (Py) and 2,7-di-tert-butylpyrene (di-t-BuPy) are reported. It was found that at a commonly employed concentration (1 mM), the ECL spectra were time-dependent because of increasing the oligomer emission and increasing the concentration of R near R*, leading to an enhancement of the excimer emission. At a low concentration range (20-30 µM), the shape of the ECL spectra containing the monomer and excimer emission was determined by isolated pairs of R* and R, which were generated through ion annihilation of R•- and R•+. It was found that in the ECL of Py and di-t-BuPy originated from the isolated pairs of R•- and R•+, 58 and 48% of the excited states were the excimer states, respectively. Diffusion equation analysis indicates that the lower excimer formation in the case of di-t-BuPy is because of a farther initial separation distance between R* and R, i.e., a longer electron transfer distance between the radical ions. The Marcus model for the electron transfer kinetics suggests that the farther electron transfer distance is mainly caused by the larger molecular size, which resulted in a smaller reorganization energy of the solvent acetonitrile molecule. Taking advantage of the photophysical and electrochemical properties of Py and di-t-Bu Py, the monomer and excimer emission in ECL is discussed.

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

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.