Near-infrared absorbing nonaromatic core-modified meta-benzicalixhexaphyrin(1.1.1.1.1.1)s

Abstract

Stable nonaromatic core-modified m-benzicalixhexaphyrins containing one m-phenylene ring, four pyrrole rings and one heterocyclic ring such as furan, thiophene, selenophene and telluorophene connected via four meso-sp² carbons and two meso-sp³ carbons in a macrocyclic framework were synthesized. The m-benzitripyrrane dicarbinol was condensed with 16-heterocycle tripyrranes under mild acid-catalyzed and inert conditions followed by open-air oxidation with DDQ to obtain macrocycles in 2-5% yields. The presence of two –OH groups in the cis-orientation at two different meso-sp³ carbons, which are adjacent to the m-phenylene ring of the macrocycle, was confirmed through detailed 1D and 2D NMR studies. NMR studies indicated that the heterocyclic ring present across the m-phenylene ring prefers to be in the inverted conformation in these macrocycles. The macrocycles exhibited two intense absorption bands in the lower wavelength region of 320–580 nm and one broad absorption band that extended from the visible to NIR region, and the protonated derivatives of such macrocycles showed significant bathochromic shifts to the NIR region. Additionally, the electrochemical studies indicated that the macrocycles underwent easier oxidation due to their electron-rich nature. DFT studies revealed that the macrocycles adopted highly distorted conformation, which was consistent with experimental results.