Influencing the self‐sorting behavior of [2.2]paracyclophane based ligands by introducing isostructural binding motifs

Autor: Volbach, Lucia, Struch, Niklas, Bohle, Fabian, Topic, Filip, Schnakenburg, Gregor, Schneider, Andreas, Rissanen, Kari, Grimme, Stefan, Lützen, Arne
Jazyk: angličtina
Rok vydání: 2020
Předmět:
Popis: 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 via 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 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. peerReviewed
Databáze: OpenAIRE