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.

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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Cobalt selenide clusters with 2-bromo-5-diethylphosphinothiophene (1) and 2-bromo-5-diphenylphosphinothiophene (2) ligands are described. The phosphine ligands are obtained via lithium halogen exchange of 2,5-dibromothiophene followed by addition of chlorodiethylphosphine and chlorodiphenylphosphine, respectively. The prepared phosphine ligands are then sequentially reacted with elemental selenium followed by dicobalt octacarbonyl to yield Co6Se8(P(Et)2(C4H2SBr))6 (3) or Co6Se8(P(Ph)2(C4H2SBr))6 (4), respectively. The two new cobalt selenide clusters were characterized by UV-visible spectroscopy, Fourier-transform infrared spectroscopy, cyclic voltammetry, powder X-ray diffraction, and elemental analysis. Emission spectra were recorded for the addition of, Co6Se8(PEt3)6 (5), 3, and 4 to a 0.004 wt% solution of poly-3-hexyl thiophene (P3HT) in toluene to investigate the charge transport of the system. The quenching of the polymers' emission follows first-order like decay for each cluster. Clusters 3 and 4 are approximately twice as efficient at quenching the emission than cluster 5 with 4 being slightly more efficient than 3. Simple mixtures of 3, 4 or 5 and P3HT were spun cast from toluene into thin films and atomic force microscopy displayed relatively uniform dispersion of 3 and network-like formation of 4 in contrast to the phase separation of 5 in the polymer films.