The inner oxygen-substituted strategy effects on structure, aromaticity and absorption spectra of corrole isomers: A theoretical study

Abstract

Corrole and oxaporphyrin have been successfully synthesized and applied in many research fields such as organic photoelectronics and sensors with the unique photophysical and chemical properties. However, the low synthesis yields of oxacorrole drive researchers turning their attention to theoretical studies for more reasonable molecular structure as the appeal of energy conservation and green chemistry. Corroles, oxacorroles (OC) and dioxacorroles (DOC), a total of 14 molecules, are calculated to systematically explore their structures, intramolecular hydrogen bonds, molecular aromatic and absorption spectral properties influenced by the inner O atoms positions with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The smaller NICS(1)_ZZ values of oxacorrole (-35.23 ppm to -33.54 ppm) and dioxacorrole (-34.91 ppm to -33.24) than these of corroles (-32.97 ppm and -33.12 ppm) indicate that the O atoms attendances can increase the molecular aromaticity. The gradually increasing energy gaps of H-8 to H-3 from Corrole1 and Corrole2 to DOC series and the larger charge of C_O (+0.208e-+0.380e) than that of C_N (+0.065e-+0.177e) illustrate that the substitution of O can reduce the degeneracy degree of energy levels and change the charge distributions. With Hirshfeld method, the molecular orbital contributions of H-1, HOMO, LUMO and L+1 exhibit the regular effects of O atoms positions on orbital energy and electron absorption spectra. For series 1, 23O is beneficial to the red shift of electron absorption spectra. These theoretical conclusions manifest that OC1-23 and DOC1-1 possess the excellent absorption characteristics in the visible region, which can be used as potential materials in the fields of photoelectric materials.

Keywords: Absorption spectra; Aromaticity; Dioxacorroles; NCI; Oxacorroles; TDDFT.