Synthesis, Structures, and Properties of Helically Fused Anthraquinones with Unusually Close Carbonyl-Carbonyl Contacts.

Abstract

Electron-deficient aromatic ketones consisting of three fused anthraquinone units were synthesized by oxidation of the corresponding fused anthracenes. X-ray analysis revealed that these compounds had nonplanar helical structures with unusual contacts, C=O⋅⋅⋅C=O 2.467 Å, between the inner carbonyl groups. The role of n⋅⋅⋅π* interactions in the short contacts was evaluated using a noncovalent interaction plot and natural bond orbital analysis. The dynamic process involving helical inversion was observed by the variable temperature 1 H NMR measurement of a derivative with 2,4,6-trimethylphenyl groups, and the barrier was estimated to be 77 kJ mol-1 . DFT calculations indicated that the helical inversion proceeded via a multistep mechanism. The characteristic spectroscopic and electrochemical data due to the electron-deficient anthraquinone units and the sterically congested carbonyl groups are discussed with the aid of DFT calculations.