Side Group of Hydrophobic Amino Acids Controls Chiral Discrimination among Chiral Counterions and Metal–Organic Cages

Abstract

The self-assembly of chiral Pd12L24 metal-organic cages (MOCs) based on hydrophobic amino acids, including alanine (Ala), valine (Val), and leucine (Leu), into single-layered hollow spherical blackberry-type structures is triggered by nitrates through counterion-mediated attraction. In addition to nitrates, anionic N-(tert-butoxycarbonyl) (Boc)-protected Ala, Val, and Leu were used as chiral counterions during the self-assembly of d-MOCs. Previously, we showed that l-Ala suppresses the self-assembly process of d-Pd12Ala24 but has no effect on l-Pd12Ala24, i.e., chiral discrimination. Here, we indicate when the amino acid used as the chiral counterion has a bulkier side group than the amino acid in the MOC structure, no chiral discrimination exists; otherwise, chiral discrimination exists. For example, Ala can induce chiral discrimination in all chiral MOCs, whereas Leu can induce chiral discrimination only in Pd12Leu24. Moreover, chiral anionic d- and l-alanine-based surfactants have no chiral discrimination, indicating that bulkier chiral counterions with more hydropohobic side groups can erase chiral discrimination.