The presence of Cu in reactions of triphenylene (TRPH) and 1,4-C4 F8 I2 at 360 °C led to regiospecific substitution of TRPH ortho C(β) atoms to form C4 F8 -containing rings, completely suppressing substitution on C(α) atoms. In addition, Cu caused selective reductive-defluorination/aromatization (RD/A) to form C4 F4 -containing aromatic rings. Without Cu, the reactions of TRPH and 1,4-C4 F8 I2 were not regiospecific and no RD/A was observed. These results, supported by DFT calculations, are the first examples of Cu-promoted 1) regiospecific perfluoroannulation, 2) preparative C-F activation, and 3) RD/A. HPLC-purified products were characterized by X-ray diffraction, low-temperature PES, and (1) H/(19) F NMR.

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.

A series of cyclometalated benzoquinoline complexes of Ir(III) catalyze the hydrogenation of the heterocyclic ring of quinolines under mild conditions. Our best catalyst is active in a significantly wider range of solvents than our previous systems. In the presence of a suitable base, the Ir(III) species is also able to hydrogenate the CO bonds of aldehydes. When quinolines and aldehydes are present together, the Ir(III) complex catalyzes a tandem reaction in which the quinoline is first hydrogenated to a tetrahydroquinoline that is subsequently reductively alkylated by the aldehyde. The reductive alkylation competes with the hydrogenation of the aldehyde to the alcohol, and therefore good yields of the alkylated tetrahydroquinoline require the presence of excess aldehyde.

What is the main focuso fy our research?We develop "top-down" synthetic methodologies for organic electron-acceptor materials that become components in aw ide variety of organic optoelectronic devices. Our syntheses are based on one-step, high-temperature, gas-or solution-phase reactions between polycyclic aromatic hydrocarbons (PAHs) and perfluoroalkyl or -aryl halides. While dozens of PAH(RF)n derivatives with electron affinities that range from 1.0 to 3.3 eV have been prepared in this manner in our lab, optimizing these reactions to produce primarily as ingle product has remained challenging until now.T his paper provides the first examples of highly selective syntheses of polysubstituted fluorous triphenylenes. Our finding that copper metal promotes specific substitution sites on triphenylene can now be applied to other PAHs ubstrates that have triphenylene-like structural elements to achieve higher selectivity in the preparation of particular PAH(RF/ArF) n targets of interest. With the myriad of fluorous PAHs at hand, we also study how various types and various numbers of fluorous groups affect their solid-state packing, which can greatly influence charge transport kinetics and thermodynamics. An unanticipated example of this is reported in this paper:r eplacing one Fa tom with an Ha tom in ac yclo-C 4 F 8 substituent resulted in ashift in columnar stacking of 508.Invited for thism onth'sc over are the groupso fS tevenS trauss/Olga Boltalina at Colorado State University,a nd Yu-Sheng Chen at the NSF'sC hemMatCARS. The cover pictures hows the evolution of fluorous triphenylenec rystalp ackingm otifs against the backdrop of the Very Large Array near Magdalena in New Mexico, where scientists studyt he evolution of the universe. The stepwise structural evolution in columnar packingo bserved was possible because of the development of a one-stepselectives ynthesis for triphenylene(C 4 F 8 ) n derivatives (n = 1-3). These compounds are expected to find application in liquid crystal displaysa nd organic electronics. Read the fulltext of the article at

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