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| - Synthesis, Electronic Structure, and Electron TransferDynamics of (Aryl)ethynyl-Bridged Donor−Acceptor Systems
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| - The ET dynamics of a series of donor−spacer−acceptor (D−Sp−A) systems featuring(porphinato)zinc(II), (aryl)ethynyl bridge, and arene diimide units were investigated by pump−probetransient absorption spectroscopy. Analysis of these data within the context of the Marcus−Levich−Jortnerequation suggests that the π-conjugated (aryl)ethynyl bridge plays an active role in the charge recombination(CR) reactions of these species by augmenting the extent of (porphinato)zinc(II) cation radical electronicdelocalization; this increase in cation radical size decreases the reorganization energy associated withthe CR reaction and thereby attenuates the extent to which the magnitudes of the CR rate constantsare solvent dependent. The symmetries of porphyrin-localized HOMO and HOMO-1, the energy gapbetween these two orbitals, and D−A distance appear to play key roles in determining whether the (aryl)ethynyl bridge simply mediates electronic superexchange or functions as an integral component of theD and A units.
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