Synthesis and characterization of macrocyclic nickel(II) complexes with α-methylbenzyl groups as chiral pendants

Novel nickel(II) hexaaza macrocyclic complexes, [Ni(LR,R)](ClO4)2 (1) and [Ni(LS,S)](ClO4)2 (2), containing chiral pendant groups have been synthesized by an efficient one-pot template condensation and characterized (LR,R/S,S = 1,8-di((R/S)-α-methylbenzyl)-1,3,6,8,10,13-hexaazacyclotetradecane). The crystal structures of 1 and 2 were determined by single-crystal X-ray analysis. Each complex has a square-planar coordination environment for the nickel(II) ion, and is either an R or an S enantiomorph depending on the pendant groups. The circular dichroism spectrum of 1 showed a negative, positive and negative peak at 345, 440, and 492 nm, respectively, and that of 2 exhibited an enantiomeric pattern.

Graphical abstractNovel hexaaza macrocyclic nickel(II) complexes, 1 and 2, containing chiral α-methylbenzyl groups have been synthesized by an efficient one-pot template condensation and characterized. The observation of the Cotton effect and the X-ray crystal structure clearly provided evidence for the chirality of 1 and 2.Figure optionsDownload full-size imageDownload as PowerPoint slide