Abstract

The first comparative DFT (B3LYP/6-31G∗) study of the Zn-porphyrin and its two derivatives, ZnP(P)4 and ZnP(As)4, is reported. For all three species studied, ZnP, ZnP(P)4 and ZnP(As)4, the singlet was calculated to be the lowest-energy structure and singlet-triplet gap was found to decrease from ca. 41 - 42 kcal/mol for N to ca. 17 - 18 kcal/mol for P and to ca. 10 kcal/mol for As. Both ZnP(P)4 and ZnP(As)4 were calculated to attain very pronounced bowl-like shapes. The frontier molecular orbitals (MOs) of the core-modified porphyrins are quite similar to the ZnP frontier MOs. For the HOMO-2 of the core-modified porphyrins due to the ZnP(P)4/ZnP(As)4 bowl-like shapes we might suppose the existence of "internal"electron delocalization inside the ZnP(P)4/ZnP(As)4 "bowls". Noticeable reduction of the HOMO/LUMO gaps was calculated for ZnP(P)4 and ZnP(As)4, by ca. 1.10 and 1.47 eV, respectively, compared to ZnP. The core-modification of porphyrins by P and especially by As was found to result in significant decrease of the charge on Zn-centers, by ca. 0.61 - 0.67e for P and by ca. 0.69 - 0.76e for As. Charges on P- and As-centers were computed to have large positive values, ca. 0.41 - 0.45e and ca. 0.43 - 0.47e, for P and As, respectively, compared to significant negative values, ca. -0.65 to -0.66e for N. The porphyrin core-modification by heavier N congeners, P and As, can noticeably modify the structures, electronic, and optical properties of porphyrins, thus affecting their reactivity and potential applications.