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 .

Corannulene Molecular Rotor with Flexible Perfluorobenzyl Blades: Synthesis, Structure and Properties.

Two members of a new class of organic-acceptor perfluorobenzyl corannulenes were prepared by gas-phase and highly-selective solution-phase reactions at elevated temperatures. The peculiar single-crystal X-ray structure of C5-C20H5(CF2C6F5)5 revealed two high-energy conformers with drastically different bowl depths and orientations of perfluorobenzyl blades; the conformers are alternating in columnar packing arrangements and every pair is sandwiched by toluene molecules.

A faux hawk fullerene with PCBM-like properties.

Reaction of C, CFCFI, and SnH(-Bu) produced, among other unidentified fullerene derivatives, the two new compounds 1,9-C(CFCF)H () and 1,9-C(-CF(2-CF)) (). The highest isolated yield of was 35% based on C. Depending on the reaction conditions, the relative amounts of and generated were as high as 85% and 71%, respectively, based on HPLC peak integration and summing over all fullerene species present other than unreacted C.

Poly(trifluoromethyl)azulenes: structures and acceptor properties.

Six new poly(trifluoromethyl)azulenes prepared in a single high-temperature reaction exhibit strong electron accepting properties in the gas phase and in solution and demonstrate the propensity to form regular π-stacked columns in donor-acceptor crystals when mixed with pyrene as a donor.

Single-step gas-phase polyperfluoroalkylation of naphthalene leads to thermodynamic products.

High-temperature gas-phase, solvent- and catalyst-free reaction of naphthalene with an excess of RF I reagent (RF CF3 , C2 F5 , n-C3 F7 , and n-C4 F9 ) was used for the first time to produce a series of highly perfluoroalkylated naphthalene products NAPH(RF )n with n=2-5. Four 95+ % pure 1,3,5,7-NAPH(RF )4 with RF CF3 , C2 F5 , n-C3 F7 , and n-C4 F9 were isolated using a simple chromatography-free procedure. These new compounds were fully characterized by (19) F and (1) H NMR spectroscopy, X-ray crystallography (for RF CF3 and C2 F5 ), atmospheric-pressure chemical ionization mass spectrometry, and cyclic and square-wave voltammetry.