Predictable Luminescence Performance of Polyphenylpyrazine Derivatives Based on Theoretical Model via Hole-Electron Overlap

Tetraphenylpyrazine (TPP), as a multi-rotor typed AIE building block with better electron-withdrawing ability, has attracted more attention due to unique photoelectric properties and wide applications of its derivatives. However, it is an urgent problem to be solved that how to predict and amplify the AIE effect of its derivatives through structural controlling. In this work, we develop a theoretical model for predicting luminescence performance of TPP derivatives where the hole-electron overlap on TPP unit is employed as a criterion with discussion based on in-depth theoretical calculations. The theoretical model indicates the larger hole-electron overlap percentage on TPP unit and the higher transition density matrix value of {TPP, TPP} will cause weaker emmision in solution and notable AIE process. Further expanding its universality in triphenylpyrazine-based derivatives, the experimental data and theoretical prediction are also very consistent, implying this model based on hole–electron overlap could be expanded to more multi-rotor AIE luminogens.