Synthesis and Studies of Fused Benzo-Benzisapphyrins

A series of rare examples of fused benzo-benzisapphyrins were synthesized readily by (3 + 2) condensation of benzodipyrrole-derived diol and para-benzitripyrrane in the presence of 0.5 equiv of TFA in CH₂Cl₂ under inert atmosphere conditions accompanied by DDQ oxidation in open air. The crude compounds were separated by basic alumina column chromatography and afforded pure fused benzo-benzisapphyrins in 20-22% yields. The fused sapphyrins were characterized in detail by high-resolution mass spectrometry (HRMS) and one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy. The ¹H NMR spectra recorded at both 298 and at 233 K clearly exhibited the presence of a strong diatropic ring current in benzo-benzisapphyrins, and the macrocycles are of aromatic nature. The DFT-optimized structure of benzo-benzisapphyrin revealed that the macrocycle was planar to a great extent due to the rigid structure of the dibenzopyrrole moiety, and the NICS(0) value of -11.2 ppm supports the aromatic nature of macrocycles. The absorption spectra of benzo-benzisapphyrins showed three weak Q bands approximately in the region of 650-900 nm and a strong Soret band at 480 nm, along with a shoulder band at ∼510 nm. The diprotonated derivative generated by the addition of excess TFA to the benzo-benzisapphyrin macrocycle exhibited bathochromically shifted absorption bands compared to the free base macrocycle.