Stoichiometry-controlled chirality inversion in the amide-linked zinc bisporphyrinates induced by amino acid esters

Abstract

We investigated chirality transfer processes with two amide-linked zinc bisporphyrinates as hosts and chiral amino acid esters as guests. The linkers in these hosts contain a coordination site (pyridyl nitrogen or amino nitrogen). CD spectra were measured after titration of these zinc bisporphyrinates with amino acid esters. The CD spectra show that the signals were inverted during the titration. This result suggests that there is a two-step chirality induction process, which is most likely dominated by the corresponding 1:1 and 1:2 host-guest complexes. In the 1:1 complexes, the pyridyl nitrogen or amino nitrogen in the linkers is coordinated with zinc. NMR spectra confirmed such coordination interactions. Theoretical calculations also confirmed the corresponding chirality induction and inversion. This work provides a useful strategy to tune chirality transfer processes by introducing an extra coordination site in the linker.