Determination of standard redox rate constants of OLED active compounds by electrochemical impedance spectroscopy

A number of commercial organic compounds (m-MTDATA, PBD, CBP, TAPC, NPB, TPBi, etc) as well as several donor-acceptor-donor (D-A-D) compounds were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The compounds were chosen as they are promising components of small-molecule-based high efficiency Thermally Activated Delayed Fluorescence (TADF) emitters in Organic Light Emitting Diodes (OLEDs). Electrochemical impedance spectra of a Pt electrode in CH₂Cl₂ solutions containing the investigated compound and Bu₄NBF₄ as the electrolyte were obtained and analyzed by electrochemical electrical circuit methods. Charge transfer resistance, double layer capacitance, Warburg constant and other parameters were determined and represented as a function of the potential. Analysis of charge transfer resistance as a function of potential allowed an estimation of standard redox rate constants for the compounds’ oxidation and reduction processes. Two main features concerning the redox reaction rates of OLED-active compounds were revealed: (i) the oxidation and reduction rates of ambipolar compounds, i.e. containing both donor and acceptor parts, were found to be much higher than those of unipolar donor-only and acceptor-only molecules; (ii) the relationship between the oxidation and reduction rate constants was shown to be related to the compounds’ conductivity type in the solid state.