Several symmetric and asymmetric1 (Figure 1) ferroceneacyl-substituted porphyrins were prepared from either direct condensation reaction between pyrrole and hexanoylferrocencarboxaldedyde or the direct cross condensation reaction between pyrrole, ferrocenecarboxaldehyde and either bromohexanoyl ferrocenecarboxaldehyde or bromoacetyl ferrocenecarboxaldehyde.1 All compounds were characterized by UV-Vis, MCD, and NMR spectroscopy. Rotational barriers of ferrocene substituents in all compounds were confirmed using variable-temperature NMR and computational methods. Density functional theory (DFT) calculations were employed to understand the geometric parameters, electronic structures, and spectroscopy of the target organometallic porphyrins. In all cases, a set of occupied predominately ferrocene-centered molecular orbitals was found between the highest occupied and the lowest unoccupied predominatly porphyrin-based molecular orbitals. The redox properties of all ferrocene-containing porphyrins were investigated in a CH2Cl2/TFAB [TFAB = tetrabutylammonium tetrakis(perfluoropphenyl)borate] system using cyclic voltammetry, differential pulse voltammetry, and square wave voltammetry methods. In all cases, oxidations of individual ferrocene substituent(s) along with porphyrin core oxidation(s) and reduction(s) have been observed. Mixed-valence complexes were formed in situ under spectro-electrochemical and chemical oxidation conditions and were characterized using UV-Vis and MCD methods. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/239nm/uploads/11254_figure1.jpg' alt='' /> 1 Vecchi, A.; Gatto, E.; Floris, B.; Conte, V.; Venanzi, M.; Nemykin, V. N. Galloni, P. Chem. Commun. 2012 , 48, 5145-5147

Long-range electronic communication in free-base 5,10,15,20-tetra(hexanoylferrocenyl)porphyrins and 5-bromoacetylferrocenyl-10,15,20-ferrocenylporphyrins

246th National Meeting (2013)

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