title: Revealing substituent effects on the electronic structure and planarity of Ni-porphyrins.
abstract: Using density functional theory, we have studied the effects on structural and electronic consequences (including HOMO-LUMO energy gaps, vertical ionization potentials (IPv), and vertical electron affinities (EAv)) of the following two factors: (a)meso- and β-substituents acting as inductive donors (CH3), inductive acceptors that are electron-donating through resonance (Br), inductive electron acceptors (CF3), and resonance enabled acceptors (NO2); and (b)complete replacementof 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 IPvand EAvnoticeably. (2) In the series CH3→ Br → CF3→ NO2the HOMO-LUMO energy gaps, IPv, and EAvincrease for bothmeso- and β-substituents. The ruffling distortion of the porphyrin core is retained, and becomes stronger for the two acceptor groups. In general, effects ofmeso-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)4, with the structural and electronic features drastically different from the original NiP. This implies that NiP(P)4can possess interesting and unusual novel properties, including aromaticity and reactivity, leading to its various beneficial potential applications. Furthermore, NiP(P)4high stability both in the gas phase and different solvents was shown, implying the feasibility of its synthesis.
authors.affiliation: Department of Chemistry, Duke University, Durham, NC 27708, USA.
authors.forename: Jenna
authors.initials: J
authors.lastname: Barbee
authors.forename: Aleksey E
authors.initials: AE
authors.lastname: Kuznetsov
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