Crowned Macrocycles Containing Two Pyrrolo[1,2-a] Indoles Created By Intramolecular Fusion.

Abstract

Heterocyclic fused-ring systems are of utmost importance because of their presence in many natural products with biological activity. Pyrroloindoles are tricyclic heterocycles that are present in various bioactive and medicinally valuable compounds. Herein, we report the synthesis of phenylene-bridged bis-pyrrolo[1,2-a]indole crowned macrocycles 1-3 in which the pyrrolo[1,2-a]indole moieties were formed via intramolecular fusion. The macrocycles were thoroughly characterized by 1D and 2D NMR, HRMS and X-ray crystallographic studies. The X-ray structure revealed that the two pyrrolo[1,2-a]indole moieties were parallel to each other, and one pyrrolo[1,2-a]indole unit was deviated by an angle of 9.54° while the other pyrrolo[1,2-a]indole unit was deviated by an angle of 12.0° from the mean plane defined by 28 core atoms. The macrocycles 1-3 absorb in the visible region and readily undergo oxidations because of their electron rich nature. The macrocycles 1-3 upon treatment with trifluoroacetic acid (TFA) generates the corresponding cation radicals 1-3.+ which were stable in the open air for a week. The cation radicals 1-3.+ absorb strongly in the NIR region and the experimental observations on crowned macrocycles 1-3 were corroborated by DFT and TD-DFT studies.