Selective self-assembly of heterodimers consisting of two non-identical subunits plays important roles in Nature but is rarely encountered in synthetic supramolecular systems. Here we show that photocleavage of a donor-acceptor porphyrin complex produces an heterodimeric structure with surprising selectivity. The system forms via a multi-step sequence that starts with an oxidative ring opening, which produces an equimolar mixture of two isomeric degradation products (zinc(II) bilatrien-abc-ones, BTOs). These two isomers are susceptible to water addition, yielding the corresponding zinc(II) 15-hydroxybiladien-ab-ones (HBDOs). However, in the photocleavage experiment only one HBDO isomer is formed, and it quantitatively combines with the remaining BTO isomer. The resulting heterodimer is stabilized by a Zn-O coordination bond and extended dispersion interactions between the overlapping π-surfaces of the monomers. The observed selectivity can be seen as a case of completive self-sorting, simultaneously controlled by three types of complementary interactions.
© 2022. The Author(s).