Theoretical Characterization of New Frustrated Lewis Pairs for Responsive Materials

In recent years, responsive materials including dynamic bonds have been widely acclaimed due to their expectation to pilot advanced materials. Within these materials, synthetic polymers have shown to be good candidates. Recently, the so-called frustrated Lewis pairs (FLP) have been used to create responsive materials. Concretely, the activation of diethyl azodicarboxylate (DEAD) by a triphenylborane (TPB) and triphenylphosphine (TPP) based FLP has been recently exploited for the production of dynamic cross-links. In this work, we computationally explore the underlying dynamic chemistry in these materials, in order to understand the nature and reversibility of the interaction between the FLP and DEAD. With this goal in mind, we first characterize the acidity and basicity of several TPB and TPP derivatives using different substituents, such as electron-donating and electron-withdrawing groups. Our results show that strong electron-donating groups increase the acidity of TPB and decrease the basicity of TPP. However, the FLP–DEAD interaction is not mainly dominated by the influence of these substituents in the acidity or basicity of the TPB or TPP systems, but by attractive or repulsive forces between substituents such as hydrogen bonds or steric effects. Based on these results, a new material is proposed based on FLP–DEAD complexes.