Synthesis, Structures, and Optical Properties of Azahelicene Derivatives and Unexpected Formation of Azahepta[8]circulenes.

Abstract

Polycyclic heteroaromatic compounds including pyrrole units are promising functional scaffolds owing to their electron-rich nature, bright fluorescence, and applicability to anion recognition at the pyrrolic hydrogen atom. We report herein the effective synthesis of pseudo-aza[5]helicene and aza[7]helicene derivatives, and unexpected formation of azahepta[8]circulenes by oxidative fusion reactions. By choosing reaction conditions and peripheral substituents attached at the terminal indole moieties, we obtained aza[7]helicenes 10 a-c and azahepta[8]circulenes 11 a,c selectively in moderate to good yields. Their solid-state structures have been revealed by X-ray diffraction analysis. UV/Vis absorption, emission, and cyclic voltammetry of these compounds were studied in comparison with those of previously reported tetraaza[8]circulene (TA8C), a symmetric and planar molecule. Furthermore, the enantiomeric separation of dimethyl-substituted aza[7]helicene 10 b was achieved, and the racemization kinetics have been elucidated both theoretically and experimentally. This work illustrates a wealth of advantages of pyrrole incorporation into the polycyclic aromatic scaffolds in terms of synthetic aspects, structural variation, and optical tuning.