Theoretical investigation on triphenylamine coelenteramide for bioinspired OLED application using thiophene rings in π-bridge

As light emitter of most marine organisms bioluminescence, coelenteramide (CLM) received much attention due to some exciting application in the field of bioinspired organic light-emitting devices (OLED). Nevertheless, native CLM only emit bright blue light. In order to obtain light of different colors, two CLM analogues, TPA-CLM and TPA-TP-CLM were designed by introduction of triphenylamine group and (thiophene) π-bridge. On the other hand, because the light emitter, CLM was produced by the chemical reaction which originates from the oxidation of bioluminescent substrate, coelenterazine (CLZ), it must be evaluated if and how substituent group tune the chemiluminescent (CL) reaction mechanism, firstly. In this article, the complete chemiluminescent reaction mechanism of TPA-CLZ and TPA-TP-CLZ and the photophysical properties of light emitters, TPA-CLM and TPA-TP-CLM were investigated by (time-dependent) density functional theory, (TD) DFT calculations. The calculations indicate that the introduction of triphenylamine and π-bridge minimally affect the complete reaction process. For the light emitters, TPA-CLM and TPA-TP-CLM, the calculation results indicate that the injection abilities of hole and electron can be largely improved by introduction of triphenylamine and π-bridge. The absorption and emission spectra appeared at longer wavelengths than native CLM. These results illustrate that TPA-CLM and TPA-TP-CLM are good candidates for bioinspired OLED application.