Synthesis and Properties of Dibenzothiophene Embedded Heteroporphyrins

A series of new stable dibenzothiophene embedded heteroporphyrins were synthesized in 6-7% yields by condensing 1 equiv of dibenzothiophene-based tripyrrane with 1 equiv of four different diols, 2,5-bis(hydroxymethyl)heterocycles (furan, thiophene, selenophene, and tellurophene), under mild acid-catalyzed conditions in CH₂Cl₂. The formation of dibenzothiophene embedded heteroporphyrins was confirmed by high-resolution mass spectrometry and thoroughly characterized by 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, absorption, electrochemical, and density functional theory/time-dependent density functional theory (DFT/TD-DFT) studies. The NMR studies indicated that the macrocycles were nonaromatic in nature. The electronic properties of the macrocycles were significantly altered as the heterocycle of the macrocycles was varied from furan to thiophene, selenophene, and tellurophene, as reflected clearly in the spectral and electrochemical properties. The macrocycles exhibited a sharp band in the region of 420-440 nm and a relatively broad absorption band(s) in the higher wavelength region of 550-800 nm. The oxa analogue was considerably blue-shifted as compared to the other macrocycles, whereas the tellura analogue exhibited relatively broadened and red-shifted absorption bands. Upon protonation of these macrocycles, the resulting diprotonated species displayed bathochromically shifted absorption bands, which were extended to the NIR region. DFT studies revealed that the macrocycles were highly distorted and strained and exhibited half chair conformation with restricted π-conjugation and confirmed their nonaromatic nature due to the lack of planarity of the macrocycle. TD-DFT studies were in agreement with the experimental spectral and electrochemical results.