Self‐Discriminating Self‐Assembly of Dinuclear Heterochiral Rhombs from Tröger’s Base Derived Bis(pyridyl) Ligands

Five racemic dissymmetric bis(pyridyl) ligands based on 2,8‐ or 3,9‐difunctionalised Tröger’s base derivatives have been synthesised. Only those derived from a 2,8‐difunctionalised scaffold were found to undergo selective self‐assembly to discrete self‐assembled dinuclear metallosupramolecular aggregates of rhomboid shape upon coordination to cis ‐protected Pd 2+ or Pt 2+ ions, as evidenced by ESI mass spectrometry, NMR spectroscopy and single‐crystal X‐ray diffraction. Interestingly, these processes were found to be highly diastereoselective leading to the formation of C 2 v ‐symmetric heterochiral assemblies in a self‐discriminating manner.