Experimental and DFT Studies of the Electron‐Withdrawing Ability of Perfluoroalkyl (RF) Groups: Electron Affinities of PAH(RF)n Increase Significantly with Increasing RF Chain Length

Two series of aromatic compounds with perfluoroalkyl (RF) groups of increasing length, 1,3,5,7‐naphthalene(RF)4 and 1,3,5,7,9‐corannulene(RF)5, have been prepared and their electronic properties studied by low‐temperature photoelectron spectroscopy (PES) (for gas‐phase electron affinity measurements). These and many related compounds were also studied by DFT calculations. The data demonstrate unambiguously that the electron‐withdrawing ability of RF substituents increases significantly and uniformly from CF3 to C2F5 to n‐C3F7 to n‐C4F9.