Biaryl-based macrocyclic and polymeric chiral (salophen)Ni(II) complexes: synthesis and spectroscopic study.

Polymeric/oligomeric and macrocyclic (salophen)Ni(II) complexes have been synthesized starting from both an achiral biphenol dialdehyde and an optically active BINOL dialdehyde. It was found that these polysalophens contain nonplanar coordination of Ni(II) units that are paramagnetic. This is different from the previously reported (salophen)Ni(II) complexes which are square planar and diamagnetic. The nonplanar (salophen)Ni(II) units make the new polymeric Ni(II) complexes different from the helical structure proposed for chiral biaryl-based polymers containing square-planar (salophen)Ni(II) units. The copolymerization of the chiral binaphthyl monomer with the achiral biphenyl monomer demonstrates that the chirality of the binaphthyl unit is not propagated along the biphenyl polymer chain.