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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.

In a simple, one-step direct trifluoromethylation of phenazine with CF3 I we prepared and characterized nine (poly)trifluoromethyl derivatives with up to six CF3 groups. The electrochemical reduction potentials and gas-phase electron affinities show a direct, strict linear relation to the number of CF3 groups, with phenazine(CF3)6 reaching a record-high electron affinity of 3.24 eV among perfluoroalkylated polyaromatics.

We report the synthesis and excited-state dynamics for a series of homoleptic copper(I) trifluoromethylated phenanthroline complexes with two, three, and four trifluoromethyl functional groups. Our analysis of the steady-state absorbance and emission, transient-absorption spectroscopy, and electronic-structure-theory calculations results enable in-depth analysis of the pseudo-Jahn− Teller distortion inhibition from increased steric hindrance of the trifluoromethyl functional group relative to the prototypical dimethyl phenanthroline complex. Surprisingly, our results demonstrate that the greatest degree of pseudo-Jahn−Teller distortion inhibition is achieved with trifluoromethylation of only the 2 and 9 positions by an unusual combination of steric hindrance and stabilization of a nondistorted 1 MLCT manifold observed by transient kinetic lifetimes and optimized excited-state structures. The intersystem-crossing (ISC) lifetime for the 2,9-bis(trifluoromethyl)-1,10phenanthroline Cu(I) complex is 69 ps, while the triplet excited-state lifetime and emission quantum yield are 106 ns and 4 × 10 −3 , respectively. Further trifluoromethylation of the phenanthroline yields a greater σ bond inductive withdrawing force on the phenanthroline nitrogens, ultimately resulting in weaker coordination to the copper. Last, the surprising success of the 2,9bis(trifluoromethyl)-1,10-phenanthroline Cu(I) complex by adjusting both ligand sterics and electronic properties outlines a new strategy for developing long-lived Cu(I) charge-transfer complexes.

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