Controlling Visible Light Driven Photoconductivity in Self-Assembled Perylene Bisimide Structures

Alanine-functionalized perylene bisimides (PBI-A) are promising photoconductive materials. PBI-A self-assembles at high concentrations (mM) into highly ordered wormlike structures that are suitable for charge transport. However, we previously reported that the photoconductive properties of dried films of PBI-A did not correlate with the electronic absorption spectra as activity was only observed under UV light. Using transient absorption spectroscopy, we now demonstrate that charge separation can occur within these PBI-A structures in water under visible light. The lack of charge separation in the films is shown by DFT calculations to be due to a large ion-pair energy in the dried samples which is due to both the low dielectric environment and the change in the site of hole-localization upon drying. However, visible light photoconductivity can be induced in dried PBI-A films through the addition of methanol vapor, a suitable electron donor. The extension of PBI-A film activity into the visible region demo...