Synthesis and Structural Properties of NIR-Absorbing Pyridine-Containing Heptaphyrins.

Four examples of stable nonaromatic pyridine containing heteroheptaphyrins (pyrithiaheptaphyrins) 2-5 were synthesized in 8-13% yields by [5+2] condensation of newly synthesized pyridine-based pentapyrrane 8 and bithiophene diol 9 a-d. The X-ray crystallographic analysis of macrocycle 2 proved that the macrocycle assumes a highly planar structure with two inverted thiophene rings. The heteroheptaphyrins 2-5 are asymmetric and showed a greater number of resonances in 1 H NMR spectra compared to our previously reported symmetric heterohexaphyrin (pyrithiahexaphyrin) 1 c. Most of the macrocyclic core protons in pyrithiahepaphyrins 2-5 experienced upfield/downfield shifts compared to pyrithiahexaphyrin 1 c indicating the alteration of π-conjugation in the macrocycles. The absorption bands were significantly red-shifted and located in the NIR region in macrocycles 2-5 compared to 1 c supporting the increase of π-delocalization. The theoretical studies support the experimental findings and NICS(0) value supports the non-aromaticity of the macrocycles.