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| - Highly Nonplanar, Electron Deficient, N-Substitutedtetra-Oxocyclohexadienylidene Porphyrinogens: Structural,Computational, and Electrochemical Investigations
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| - The structures and electrochemistry of N-benzylated meso-tetrakis (3,5-di-tert-butyl-4-oxo-cyclohexa-2,5-dienylidene) porphyrinogens have been investigated. Structural determinations reveal theisomeric identity of the products obtained from the N-alkylation of the parent meso-tetra (oxo-cyclohexadienylidene) porphyrinogen. The compounds are subject to increased macrocyclic deformations upon increasing N-substitution culminating in the tetra-N-benzyl derivative, which has abuckling superimposed on the already highly puckered macrocycle. The electrochemical analysesemphasize the electron deficiency of the N-benzylated meso-tetra(oxo-cyclohexadienylidene) porphyrinogens and indicate that they can be considered as quinones conjugated via the unsaturatedtetrapyrrolic macrocycle. The N-benzylated compounds studied form stable and well-defined π-cationradical and π-anion radical species because of their highly conjugated nature. Ab initio molecularorbital calculations at the B3LYP/3-21G(*) level confirmed the high degree of conjugation betweentetrapyrrole and meso substituents and also gave good agreement between calculated andexperimentally determined HOMO−LUMO band gap energies.
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