Influencing the Self‐Sorting Behavior of [2.2]Paracyclophane‐Based Ligands by Introducing Isostructural Binding Motifs

Two isostructural ligands with either nitrile (L(nit)) or isonitrile (L(iso)) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself (L(nit)) or its precursors (L(iso)) were resolved by HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental electronic circular dichroism (ECD) spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf)(2)] differ in their composition: whereas L(nit) forms dinuclear complexes, L(iso) exclusively forms trinuclear ones. Furthermore, they also differ in their chiral self‐sorting behavior as (rac)‐L(iso) undergoes exclusive social self‐sorting leading to a heterochiral assembly, whereas (rac)‐L(iso) shows a twofold preference for the formation of homochiral complexes in a narcissistic self‐sorting manner as proven by ESI mass spectrometry and NMR spectroscopy. Interestingly, upon crystallization, these discrete aggregates undergo structural transformation to coordination polymers, as evidenced by single‐crystal X‐ray diffraction.