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Updated: Sep 20, 2025

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
Synthesis of a donor-acceptor heterodimer via trifunctional completive self-sorting
Sunit Kumar1, Yogesh Kumar Maurya1, Tadeusz Lis1
1Wydział Chemii, Uniwersytet Wrocławski, ul. F. Joliot-Curie 14, 50-383, Wrocław, Poland.
Abstract:
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.
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