Di-2,7-pyrenidecaphyrin(1.1.0.0.0.1.1.0.0.0) and Its Bis-Organopalladium Complexes: Synthesis and Chiroptical Properties

Abstract

A non-aromatic expanded carbaporphyrinoid, incorporating two built-in 2,7-pyrenylene moieties was synthesized. The intrinsically labile structure was demonstrated by proton-triggered conformational changes between the figure-of-eight and quasi-Möbius conformers. Upon treatment with Pd(OAc)₂ , the reaction produces two bis-Pd^II complexes with distinct coordination modes. Metal coordination serves to fix the macrocyclic frameworks with the net result that both bis-Pd^II complexes could be resolved by high performance liquid chromatography (HPLC) on a chiral stationary phase. The isolated enantiomers showed persistent chiroptical properties as evidenced by the intense response in the circular dichroism (CD) spectra and the record high absorption dissymmetry factors (g_abs of up to 0.038) seen in the near-infrared spectral region. Moreover, the mutual interconversion of these two Pd^II complexes was found to be stereospecific and to favor the more stable isomers under weakly acidic conditions.

Keywords: Chiral Resolution; Chiroptical Properties; Expanded Porphyrin; Organopalladium Complexes; Pyrene.