A large number of ferrocene-containing aza-BODIPYs, BODIPYs, subphthalocyanines, and porphyrins have been prepared and characterized by UV-Vis-NIR, MCD, NMR, APCI MS/MS, and X-ray crystallography.1-3 The redox properties of target compounds were investigated by electrochemical and spectroelectrochemical methods as well as by the chemical oxidation using variety of oxidants. Fluorescence properties and non-radiative decay pathways were investigated by steady-state and time-resolved techniques in the picosecond and femtosecond regimes. Influence of the metallocenyl substituents' coordination mode (i.e. peripheral vs. axial connectivity; direct vs. trough spacer connectivity) on formation of the redox-induced mixed-valence and photoinduced charge separation states will be discussed. The experimental electronic, spectroscopic, and geometric parameters of neutral, mixed-valence, and charge separated states in the metallocenyl-containing aromatic macrocycles will be correlated with DFT and TDDFT calculations.References:(a)Nemykin, V. N.; Purchel, A. A.; Spaeth, A. D.; Barybin, M. V. Inorg. Chem., 2013 , 52, 11004. (b) Dammer, S. J.; Solntsev, P. V.; Sabin, J. R.; Nemykin, V. N. Inorg. Chem. 2013 , 52, 9496.P. V. Solntsev, J. R. Sabin, S. J. Dammer, N. N. Gerasimchuk, and V. N. Nemykin, Chem. Commun. 2010 , 6581.P. V. Solntsev, K. L. Spurgin, J. R. Sabin, A. A. Heikal, and V. N. Nemykin, Inorg. Chem. 2012 , 51, 6537.

Redox-driven fluorescence and photo-induced electron transfer in organometallic supramolecular dyads and triads with porphyrin, subphthalocyanine, BODIPY, and azaBODIPY chromophores

248th National Meeting (2014)

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