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The use of biomaterials - with techniques such as DNA-directed assembly orbio-directed synthesis - can surpass top-down fabrication techniques increating plasmonic superstructures, in terms of spatial resolution, range offunctionality and fabrication speed. Particularly, by enabling a very preciseplacement of nanoparticles in a bio-assembled complex or a controlledbio-directed shaping of single nanoparticles, plasmonic nanocrystals can showremarkably strong circular dichroism (CD) signals. Here we show that chiralbio-plasmonic assemblies and nanocrystals can enable polarization-sensitivephotochemistry based on the generation of energetic (hot) electrons. It is nowestablished that hot plasmonic electrons can induce surface photochemistry oreven reshape plasmonic nanocrystals. Here we show that merging chiral plasmonicnanocrystal systems and the hot-election generation effect offers uniquepossibilities in photochemistry - such as polarization-sensitive photochemistrypromoting nonchiral molecular reactions, chiral photo-induced growth of acolloid at the atomic level and chiral photochemical destruction of chiralnanocrystals. Regarding practical applications, our study suggests interestingopportunities in polarization-sensitive photochemistry, chiral recognition orseparation, and in promoting chiral crystal growth at the nanoscale.

Chiral plasmonic nanocrystals for generation of hot electrons: towards polarization-sensitive photochemistry