Beschreibung:
<jats:title>Abstract</jats:title><jats:p>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 <jats:italic>cis</jats:italic>‐protected Pd<jats:sup>2+</jats:sup> or Pt<jats:sup>2+</jats:sup> 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 <jats:italic>C</jats:italic><jats:sub>2<jats:italic>v</jats:italic></jats:sub>‐symmetric heterochiral assemblies in a self‐discriminating manner.</jats:p>