Revealing substituent effects on the electronic structure and planarity of Ni-porphyrins.

Using density functional theory, we have studied the effects on structural and electronic consequences (including HOMO-LUMO energy gaps, vertical ionization potentials (IP), and vertical electron affinities (EA)) of the following two factors: (a) - and β-substituents acting as inductive donors (CH), inductive acceptors that are electron-donating through resonance (Br), inductive electron acceptors (CF), and resonance enabled acceptors (NO); and (b) of pyrrole nitrogens with P-atoms. The principal results of the study are: (1) For the bare Ni-porphyrin, the solvents were found not to affect the HOMO-LUMO gaps but to change the IP and EA noticeably. (2) In the series CH → Br → CF → NO the HOMO-LUMO energy gaps, IP, and EA increase for both - and β-substituents. The ruffling distortion of the porphyrin core is retained, and becomes stronger for the two acceptor groups. In general, effects of -substituents on the ruffling distortion of the porphyrin core is more pronounced. (3) Most significantly, complete replacement of pyrrole nitrogens in the NiP with phosphorus atoms produces the species, NiP(P), with the structural and electronic features drastically different from the original NiP. This implies that NiP(P) can possess interesting and unusual novel properties, including aromaticity and reactivity, leading to its various beneficial potential applications. Furthermore, NiP(P) high stability both in the gas phase and different solvents was shown, implying the feasibility of its synthesis.