Helicenes are very attractive chiral non-planar polycyclic aromatic hydrocarbons possessing strong chiroptical properties. However, most of the helicenes absorb light mainly in the ultraviolet region, with only a small segment in the blue part of the visible spectrum. Furthermore, carbo[n]helicenes exhibit only weak luminescence that limits their utilization. Herein, we demonstrate that peripheral decoration of the helicene backbone with an aryl-carbonyl group shifts the absorption to the visible region and simultaneously improves their fluorescence quantum yields. We thus show that the carbonyl group, commonly considered as detrimental to emission, has the capability of improving optical and photophysical properties. Two different families, aceno[n]helicenones and fluoreno[n]helicenes, are presented with comprehensive spectrochemical characterization. TD-DFT calculations were implemented to clarify their electronic profiles. We show that increasing the helical length in aceno[n]helicenes increases absorption onset, g abs and g lum. Extension of the peripheral aromatic part in fluoreno[n]helicenes leads to a blue shift in both absorption and emission.

Institut de Chimie et Biologie des Membranes et des Nanoobjets Université de Bordeaux INP UMR 5248 Allée St Hilaire 33607 Pessac Cedex France

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences 166 10 Prague 6 Czech Republic

Institute of Physics Polish Academy of Sciences Al Lotników 32 46 02 668 Warsaw Poland

Japan Institute for Chemical Reaction Design and Discovery Hokkaido University Sapporo Hokkaido 001 0021 Japan

Université de Bordeaux CNRS Centre de Recherche Paul Pascal CRPP UMR 5031 33600 Pessac France

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