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.

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. DFT calculations confirm that the proposed synthesis yields the most stable isomers that have not been accessed by alternative preparation techniques.

Faux‐hawk fullerenes are promising candidates for high‐performance organic field‐effect transistors (OFETs). They show dense molecular packing and high thermal stability. Furthermore, in contrast to most other C60 derivates, functionalization of the fullerene core by the fluorinated group C6F4CF2 does not increase their lowest unoccupied orbital position, which allows the use of air‐stable molecular n‐dopants to optimize their performance. The influence of n‐doping on the performance of OFETs based on the faux‐hawk fullerene 1,9‐C60(cyclo‐CF2(2‐C6F4)) (C60FHF) is studied. An analytic model for n‐doped transistors is presented and used to clarify the origin of the increase in the subthreshold swing usually observed in doped OFETs. It is shown that the increase in subthreshold swing can be minimized by using a bulk dopant layer at the gate dielectric/C60FHF layer instead of a mixed host:dopant layer. Following an optimization of the OFETs, an average electron mobility of 0.34 cm2 V−1 s−1, a subthreshold swing below 400 mV dec−1 for doped transistors, and a contact resistance of 10 kΩ cm is obtained, which is among the best performance for fullerene based n‐type semiconductors.

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.