Structural Gating Enhances Long-Distance Light-Driven Interfacial Electron Transfer

Structural gating provides a molecular means to transfer electrons preferentially in one desired vectorial direction, a behavior needed for applications in artificial photosynthesis. At the interfaces utilized herein, visible-light absorption by a transition metal complex <i>opens</i> a "structural gate" by planarization of otherwise rotating phenyl rings in <i>p-</i>phenylene ethynylene (PE) bridge units. Planarization provides a conjugated pathway for electron flow toward a conductive oxide surface. Interfacial electron transfer to the oxide restores rotation and <i>closes</i> the gate to the unwanted recombination reaction. This structural gating results in nearly quantitative long-distance (>20 Å) interfacial electron transfer that occurs ∼1000 times faster than transfer in the opposite direction. A comparative kinetic study of these complexes with those that contain ionic bridge units, without gating function, as a function of the applied potential and hence -Δ<i>G</i>° provided a physical basis for the structural gating. A small distance-dependent reorganization energy with weak electronic coupling underlies the success of this gate that enables efficient long-distance electron transfer and slow recombination.