Experimental and DFT Studies of the Electron-Withdrawing Ability of Perfluoroalkyl (R ) Groups: Electron Affinities of PAH(R ) Increase Significantly with Increasing R Chain Length.

Two series of aromatic compounds with perfluoroalkyl (R ) groups of increasing length, 1,3,5,7-naphthalene(R ) and 1,3,5,7,9-corannulene(R ) , 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 R substituents increases significantly and uniformly from CF to C F to n-C F to n-C F .