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

Long K San; Sarah N Spisak; Cristina Dubceac; Shihu H M Deng; Igor V Kuvychko; Marina A Petrukhina; Xue-Bin Wang; Alexey A Popov; Steven H Strauss; Olga V Boltalina

doi:10.1002/chem.201704868

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

Chemistry. 2018 Jan 26;24(6):1441-1447. doi: 10.1002/chem.201704868. Epub 2017 Dec 19.

Affiliations

¹ Department of Chemistry, Colorado State University, Fort Collins, Colorado, 80523, USA.
² Department of Chemistry, University at Albany, State University of New York, Albany, New York, 12222, USA.
³ Physical Sciences Division, Pacific Northwest National Laboratory, MS K8 88, P.O. Box 999, Richland, Washington, 99352, USA.
⁴ Department of Electrochemistry and Conducting Polymers, Liebniz Institute for Solid State and Materials Research, Dresden, 01069, Germany.

PMID: 29178382
DOI: 10.1002/chem.201704868

Abstract

Two series of aromatic compounds with perfluoroalkyl (R_F ) groups of increasing length, 1,3,5,7-naphthalene(R_F )₄ and 1,3,5,7,9-corannulene(R_F )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 R_F substituents increases significantly and uniformly from CF₃ to C₂ F₅ to n-C₃ F₇ to n-C₄ F₉ .

Keywords: density functional calculations; electron affinity; fluorine; perfluoroalkyl; polyaromatic hydrocarbons.