Computational Modeling of Next Generation Quinazolinespirohexadienones for Application as Photochromic Photooxidants

Our group’s ongoing research program focuses on designing more reducible analogs of the perimidinespirohexadienone (PSHD) photochromes as potential photochromic photooxidants capable of gating the molecules’ ability to initiate photoinduced charge transfer reactions for possible materials applications. Replacing the naphthalene moiety of the PSHDs with a quinoline moiety gives the quinazolinespirohexadienone (QSHD) family of photochromes whose synthesis, photochemistry, and electrochemistry we have recently reported. In this work we describe recent computational efforts on the MU3C cluster to design even more electron deficient QSHD analogs capable of gating PICT and photooxidizing less reducible monomers of interest to materials applications. We report computed reduction potentials based on our present methodology and investigate application of our newly reported methodology to photochromes. We also use bond order, bond length and molecular orbital calculations to predict the likely direction of spirocyclic ring opening for these asymmetric photochromes