Supramolecular device for 1D energy/electron transfer through a helical channel

ORGN 279

Oh-Kil Kim, oh.kim@nrl.navy.mil1, Mike F. Pepitone, michael.pepitone@nrl.navy.mil1, Joseph S. Melinger, joseph.melinger@nrl.navy.mil2, and Glenn G. Jernigan, glenn.jernigan@nrl.navy.mil2. (1) Chemistry Division and Institute for Nanoscience, Naval Research Laboratory, 4555 Overlook Ave, S.W, Washington, DC 20375-5320, (2) Electronics Science & Technology Division and Institute for Nanoscience, Naval Research Laboratory, 4555 Overlook Ave, S.W, Washington, DC 20375-5320
Photo-/electroactive donor-acceptor (D-A) chromophores were designed/synthesized and investigated for energy- and electron-transfer (ET/eT). The chromophores are supramolecularly integrated into helical cavity of amylose to generate a single molecular encapsulation by the helix. This renders the chromophore rigidified along the helical axis and aggregation-free, leading to a remarkable fluorescence enhancement. ET/eT of the D-A chromophores were investigated using fluorescence quenching in the presence and absence of the helical encapsulation, and the transporting properties are discussed with respect to D-A distance, D/A strength and solvent effect. ET/eT of the encapsulated chromophores show a clear dependence on D-A distance, while those of the encapsulation-free counterparts have no discrete distance dependence, suggesting that the fluorescence quenching involves other quenching sources including aggregations than ET/eT. Such differences in ET/eT behavior are well reflected in their florescence decay profile. Another notable difference is that the helical supramolecule of the chromophores is capable of a self-assembly, whereas either the free chromophores or the helix alone is unable to do. The assembly features and substrate binding are also discussed.