Selective Photoactivation of Trithiocarbonates Mediated by Metal Naphthalocyanines and Overcoming Activation Barriers Using Thermal Energy.

Abstract

Metal naphthalocyanines (MNcs) were demonstrated to be efficient photocatalysts to activate photoinduced electron-transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, enabling well-controlled polymerization of (meth)acrylates under near-infrared (λ = 780 nm) light. Owing to their lower redox potential compared to previously explored photocatalysts, the activation of trithiocarbonate RAFT agents exhibited a unique selectivity that was dependent on the nature of the R group. Specifically, MNcs were capable in activating tertiary R group trithiocarbonates, whereas no activation of the trithiocarbonate possessing a secondary R group was observed. The combination of density functional theory calculations and experimental studies have revealed new mechanistic insights into the factors governing a PET-RAFT mechanism and explained this unique selectivity of MNcs toward tertiary carbon trithiocarbonates. Interestingly, by increasing the reaction temperature moderately (i.e., ∼15 °C), the energy barrier prohibiting the photoactivation of the trithiocarbonate with a secondary R group was overcome, enabling their successful activation.