[<i>n</i>]‐Cyclo‐9,9‐dibutyl‐2,7‐fluorene (<i>n</i>=4, 5): Nanoring Size Influence in Carbon‐Bridged Cyclo‐<i>para</i>‐phenylenes
Lambert Sicard, Fabien Lucas, Olivier Jeannin, Pierre‐Antoine Bouit, Joëlle Rault‐Berthelot, Cassandre Quinton, Cyril Poriel
Abstract
For the last ten years, ring-shaped π-conjugated macrocycles possessing radially directed π-orbitals have been subject to intense research. The electronic properties of these rings are deeply dependent on their size. However, most studies involve the flagship family of nanorings: the cyclo-para-phenylenes. We report herein the synthesis and study of the first examples of cyclofluorenes possessing five constituting fluorene units. The structural, optical and electrochemical properties were elucidated by X-ray crystallography, UV-vis absorption and fluorescence spectroscopy, and cyclic voltammetry. By comparison with a shorter analogue, we show how the electronic properties of [5]-cyclofluorenes are drastically different from those of [4]-cyclofluorenes, highlighting the key role played by the ring size in the cyclofluorene family.