Helicates of Chiragen-Type Ligands and Their Aptitude for Chiral Self-Recognition

Two (-)-5,6-pinene-bipyridine moieties connected by a para-xylylene bridge (so-called chiragen-type ligands), (-)-L1, undergo self-assembly upon reaction with equimolar amounts of CuI to form enantiopure circular hexanuclear P-helicates. If both enantiomers of L1 are used, mixtures of P and M hexanuclear helicates are exclusively obtained through a complete chiral recognition; that is, no mixing of the (+) and (-) ligands, respectively, occurs upon complexation. This was proven by a) NMR spectroscopy where identical spectra to those for complexes with the enantiomerically pure ligands were obtained and b) circular dichroism (CD) spectroscopy. The reaction is completely changed by the use of the corresponding meso-L1. Instead of well-defined species, oligomeric mixtures are observed, a result demonstrating the crucial role played by ligand chirality in self-assembly processes. Structural variations on the chiral ligand L1, such as a meta-xylylene bridge instead of a para-xylylene one (in L4) or four pinene groups instead of two (in L5 and L6), favor nondiscrete coordination assembly.