Redox-active Star Molecules Incorporating the 4-benzoylpyridinium Cation: Implications for the Charge Transfer Efficiency Along Branches vs. Across the Perimeter in Dendrimers
We report the redox properties of four star systems incorporating the 4-benzoyl-N-alkylpyridinium cation; the redox potential varies along the branches but remains constant at fixed radii. Bulk electrolysis shows that at a semi-infinite time scale all redox centers are electrochemically accessible. However, voltammetric analysis (cyclic voltammetry and differential pulse voltammetry) shows that only two of the three redox-active centers in the perimeter are electrochemically accessible during potential sweeps as slow as 20 mV s-1 and as fast as 10 V s-1. On the contrary, both redox centers along branches are accessible electrochemically within the same time frame. These results are explained in terms of slow through-space charge transfer and the globular 3-D folding of the molecules and are discussed in terms of their implications on the design of efficient redox functional dendrimers.
N. Leventis et al., "Redox-active Star Molecules Incorporating the 4-benzoylpyridinium Cation: Implications for the Charge Transfer Efficiency Along Branches vs. Across the Perimeter in Dendrimers," Journal of American Chemical Society, American Chemical Society (ACS), Mar 2004.
NASA Glenn Research Center Director's Discretionary Fund (DDF)
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