Probing Exciton Delocalization in Organic Semiconductors: Insight from Time-Resolved Electron Paramagnetic Resonance and Magnetophotoselection Experiments

Delocalization of excited states of organic semiconductors is directly related to their efficiency in devices. Time-resolved electron paramagnetic resonance spectroscopy provides unique capabilities in this respect because of its high spectral resolution and capability to probe the geometry and extent of excitons. Using magnetophotoselection experiments, the mode of exciton delocalization, along the backbone or parallel to the π−π stacking direction of the conjugated polymers, can be revealed. We demonstrate the robustness of this approach by applying it to building blocks of a prototypical conjugated polymer showing a symmetry of their excited states being far from ideal for this experiment. This renders magnetophotoselection superior to other approaches because it is applicable to a wealth of other organic semiconductors. The insight gained into exciton delocalization is crucial to the structure−function relationship of organic semiconductors and directly relevant for developing highly efficient materials.