We determine the presence of four open-form configurational isomers for an unsubstituted metastable-state photoacid (mPAH) of the tricyanofuran (TCF) type in solution, at room temperature, via 2D NMR experiments. Electronic structure calculations are carried out to predict the relative stability of the isomers found experimentally and their isomerization barriers. According to the calculated rate constants for isomerization, the molecule can freely interconvert between the open-form isomers, thereby providing a thermal pathway between the isomers that might be better suited to access the cyclized closed-form configuration and those that are not. In establishing the open form isomeric makeup of the TCF mPAH under study, this work establishes the need to consider the four isomers in further studies on the thermal and excited-state isomerization processes and substituent effect thereon.
© 2022 The Authors. Published by American Chemical Society.