Effects of Core Modification on Electronic Properties of para-Benziporphyrins.

Abstract

In contrast to the nonaromatic meta-benziporphyrins, the para-benziporphyrins possess aromatic character depending on the type of five-membered ring present in the macrocyclic core. The effects of changing the para-benziporphyrinic core from C2N3 to C2NSN, C2NSeN, and C2NTeN by replacing the pyrrole with other five-membered heterocycles such as thiophene, selenophene, and tellurophene on aromatic properties of p-benziporphyrins are described here using spectral, electrochemical, X-ray, and density functional theory (DFT) studies. The missing core-modified p-benziporphyrins with C2NSeN and C2NTeN cores were synthesized by condensing 1 equiv of benzitripyrrane and 1,3-benzene-bis((4-phenyl)methanol with an appropriate diol such as 2,5-bis[(p-tolyl)hyroxymethyl]selenophene and 2,5-bis(hydroxymethyl)tellurophene under mild acid-catalyzed conditions at room temperature and characterized in detail by high-resolution mass spectrometry (HR-MS), one- & two-dimensional NMR, and X-ray crystallography of the one of the macrocycles, Selena p-benziporphyrin. The X-ray structure of Selena p-benziporphyrin revealed that the macrocycle was almost planar apart from the p-phenylene ring, which was deviated by 49.71° from the mean plane of the macrocycle defined by four meso carbons, unlike Selena m-benziporphyrin, which is relatively more distorted. NMR studies revealed that, as the core changes from C2N3 to C2NSN, C2NSeN, and C2NTeN, the diatropic ring current decreases, indicating that the aromatic character also decreases in the same order. X-ray structure and DFT studies also revealed that the distortion in the macrocycle increases as the pyrrole ring of p-benziporphyrin was replaced with other heterocycles such as furan, thiophene, selenophene, and tellurophene and that the tellura p-benziporphyrin was the most distorted macrocycle among core-modified p-benziporphyrins. Absorption and electrochemical properties were in agreement with these observations. Our repeated attempts on metalation of these p-benziporphyrins resulted in the successful synthesis of a Pd(II) complex of tellura p-benziporphyrin. The Pd(II) complex was characterized by HR-MS and NMR techniques, and the structure was optimized by DFT. The studies indicated that the Pd(II) ion was bonded to one of the pyrrolic nitrogens, tellurophene, tellurium, and two chloride ions in distorted square-planar geometry.