Reversible catenation of coordination rings with Pd(II) and/or Pt(II) metal centers: Chirality induction through catenation

Abstract

AbstractA Pd(II)‐linked coordination ring is reversibly transformed into its catenanted dimer at room temperature through the efficient organic stacking of the component rings. An analogous Pt(II)‐linked ring is also catenated only at high temperature (100 °C), but not at room temperature because of the kinetic inertness of Pt(II)‐ligand interaction. Interestingly, the combination of the Pd(II)‐ and the Pt(II)‐linked coordination rings selectively gives a Pd(II)/Pt(II) cross‐catenane, because the kinetically inert Pt(II) ring can be catenated only via the dissociation of the kinetically labile Pd(II) ring. Planer conformation of the monomer rings is twisted upon catenation, inducing helical chirality in the catenated structure. Thus, induced circular dichroism (ICD) is observed in the catenation when chiral‐1,2‐cyclohexandiamine is attached as a chiral auxiliary on the metal centers. The ICD decreases with increasing temperature due to less effective chiral aromatic stacking at higher temperature. The Pd(II) ring shows higher ICD than the Pt(II) ring, probably due to the more flexible conformation of the Pd(II) ring that can adopt chiral orientation easily. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3478–3485, 2003