Hendriksenwillis7271

The interaction of free-base triarylcorroles with Re2(CO)10 in 1,2-dichlorobenzene in the presence of 2,6-lutidine at 180 °C under strict anerobic conditions afforded approximately 10% yields of rhenium corrole dimers. The compounds exhibited diamagnetic 1H NMR spectra consistent with a metal-metal quadruple bond with a σ2π4δ2 orbital occupancy. One of the compounds proved amenable to single-crystal X-ray structure determination, yielding a metal-metal distance of ∼2.24 Å, essentially identical to that in triple-bonded osmium corrole dimers. On the other hand, the electrochemical properties of Re and Os corrole dimers proved to be radically different. Thus, the reduction potentials of the Re corrole dimers are some 800 mV upshifted relative to those of their Os counterparts. Stated differently, the Re corrole dimers are dramatically easier to reduce, reflecting electron addition to δ* versus π* molecular orbitals for Re and Os corrole dimers, respectively. The data also imply electrochemical HOMO-LUMO gaps of only 1.0-1.1 V for rhenium corrole dimers, compared with values of 1.85-1.90 V for their Os counterparts. These HOMO-LUMO gaps rank among the first such values reported for quadruple-bonded transition-metal dimers for any type of supporting ligand, porphyrin-type or not.Ionic liquids (IL) are valuable in a variety of applications due to their high electrochemical stability and physical properties. Using the cation 1-methyl-3-octylimidazolium, [OMIM]+, the bromidostannate RTIL [OMIM][Sn+IIBr3], "undercooled melt" [OMIM][Sn+IVBr5], and IL [OMIM]2[Sn+IVBr6] were synthesized. The uncommon solid state structure of [SnBr5]- was elucidated in the form of its RTIL salt. Additionally, the IL based on tribromine-monoanion [OMIM][Br3] was used to dissolve metallic Sn, selectively resulting in the formation of [SnBr3]- as confirmed by Raman spectroscopy. Subsequent cyclic voltammograms (CV) of [SnBr3]- confirmed the deposition potential of metallic Sn and renewal of the polybromide [Br3]-. The RTIL bromidostannates were stable compounds, making a selective electrochemical investigation of the deposition of metallic Sn(0) to Sn(+II)/Sn(+IV) redox process possible, via conductance and CV measurements. The CVs of the RTILs and of solutions in propylene carbonate had the redox couples of Sn(0)/[Sn+IIBr3]-/[Sn+IVBr5]-.In studies of tobacco toxicology, including comparisons of different tobacco products and exposure to secondhand or thirdhand smoke, exposure assessment using biomarkers is often useful. Some studies have indicated that most of the toxicity of tobacco smoke is due to gas-phase compounds. 3-Ethenylpyridine (3-EP) is a major nicotine pyrolysis product occurring in the gas phase of tobacco smoke. It has been used extensively as an environmental tracer for tobacco smoke. 3-EP would be expected to be a useful tobacco smoke biomarker as well, but nothing has been published about its metabolism and excretion in humans. In this Article we describe a solid-phase microextraction (SPME) GC-MS/MS method for determination of 3-EP in human urine and its application to the determination of 3-EP in the urine of smokers and people exposed to secondhand smoke. We conclude that 3-EP is a promising biomarker that could be useful in studies of tobacco smoke exposure and toxicology. We also point out the paucity of data on 3-EP toxicity and suggest that additional studies are needed.Hybrid devices consisting of graphene or transition metal dichalcogenides (TMDs) and semiconductor quantum dots (QDs) were widely studied for potential photodetector and photovoltaic applications, while for photodetector applications, high internal quantum efficiency (IQE) is required for photovoltaic applications and enhanced carrier diffusion length is also desirable. Here, we reported the electrical measurements on hybrid field-effect optoelectronic devices consisting of compact QD monolayer at controlled separations from single-layer graphene, and the structure is characterized by high IQE and large enhancement of minority carrier diffusion length. While the IQE ranges from 10.2% to 18.2% depending on QD-graphene separation, ds, the carrier diffusion length, LD, estimated from scanning photocurrent microscopy (SPCM) measurements, could be enhanced by a factor of 5-8 as compared to that of pristine graphene. SAR405 in vivo IQE and LD could be tuned by varying back gate voltage and controlling the extent of charge separation from the proximal QD layer due to photoexcitation. The obtained IQE values were remarkably high, considering that only a single QD layer was used, and the parameters could be further enhanced in such devices significantly by stacking multiple layers of QDs. Our results could have significant implications for utilizing these hybrid devices as photodetectors and active photovoltaic materials with high efficiency.A general aminoalkylation of aryl halides was developed, overcoming intolerance of free amines in nickel-mediated C-C coupling. This transformation features broad functional group tolerance and high efficiency. Taking advantage of the fast desilylation of α-silylamines upon single-electron transfer (SET) facilitated by carbonate, α-amino radicals are generated regioselectively, which then engage in nickel-mediated C-C coupling. The reaction displays high chemoselectivity for C-C over C-N bond formation. Highly functionalized pharmacophores and peptides are also amenable.Modifying molecular conjugation has been demonstrated as an effective strategy to enhance the photovoltaic performance of the non-fullerene small molecule acceptors (SMAs), which would regulate the molecular packing and nanoscale morphology in the active layer of organic solar cells (OSCs). Here, two novel SMAs PTIC-4Cl and PT2IC-4Cl are designed and synthesized by expanding the core unit of TB-4Cl in one or two directions. The effects of how to expand the conjugation length on the absorption property, energy levels, dipole moment, and solubility are studied via theoretical calculation and experiments. Compared to PT2IC-4Cl, PTIC-4Cl with a more asymmetric structure exhibits the larger dipole moment and enhanced intermolecular packing. The PTIC-4Cl-based OSCs exhibit a favorable morphology and balanced charge transport, thereby leading to the highest power conversion efficiencies. In addition, PTIC-4Cl-based devices show outstanding thermal and air stability. These results reveal that fine-tuning the dipole moment via rationally expanding the conjugation in asymmetric A-D1A'D2-A-type non-fullerene acceptors is critical to achieve high-performance OSCs.