Heterochiral Self‐Discrimination‐Driven Supramolecular Self‐Assembly of Decanuclear Gold(I)‐Sulfido Complexes into 2D Nanostructures with Chiral Anions‐Tuned Morphologies

Abstract

Chiral self-recognition and self-discrimination are of vital importance to biological processes. In this work, 2D regular rhombic nanocrystals (RS-NC) were fabricated through heterochiral self-discrimination between chiral polynuclear gold(I)-sulfido complex enantiomers, [(R-BINAP)4Au10S4]Cl2 (R-Au10) and [(S-BINAP)4Au10S4]Cl2 (S-Au10), in MeOH without the need for any surfactants or templates. The monitoring of nanocrystals (NCs) formation by TEM and DLS has uncovered the self-assembly process and shape evolution of the NCs and revealed a screw-dislocation dictated spiral growth of the rhombic NCs. Upon addition of chiral anions, the morphology of the gold NCs was found to change from rhombic to strip and quasi-hexagonal nanosheets, arising from reverse and rotational layer-by-layer stacking to give the bilayer NCs. By applying a high temperature, rhombic gold nanoisland films were obtained from the rhombic NCs. The current study has provided a simple strategy towards the construction of regular geometric 2D NCs as well as their chiral anion-tuned and reverse and rotational stacking-determined morphology change by heterochiral self-discrimination.