Synthesis and photovoltaic behaviors of narrow‐band‐gap π‐conjugated polymers composed of dialkoxybenzodithiophene‐ and thiophene‐based fused aromatic rings

π‐Conjugated polymers, PBDT‐CNETT and PBDT‐CNECPDT , were prepared by the Stille cross‐coupling polymerization. Optical and thermal properties of the obtained polymers were investigated by UV–vis spectroscopy and thermogravimetric analysis. PBDT‐CNETT and PBDT‐CNECPDT exhibited very narrow band gaps of 1.39 and 1.13 eV, respectively. Highest occupied molecular orbital energy levels estimated by surface analyzer were ?5.17 and ?5.11 eV for PBDT‐CNETT and PBDT‐CNECPDT , respectively. The solar cells based on these polymers were evaluated with the cell configuration of ITO/PEDOT‐PSS/polymer:PC₆₁BH/LiF/Al. The power conversion efficiencies of the solar cells were estimated to be 1.57 and 0.16% for PBDT‐CNETT and PBDT‐CNECPDT , respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Upper Limit of Nitrogen Content in Carbon Materials

Nitrogen‐doped carbon materials (NDCs) play an important role in various fields. A great deal of effort has been devoted to obtaining carbon materials with a high nitrogen content; however, much is still unknown about the structure of the nitrogen‐doped materials and the maximum nitrogen content possible for such compounds. Here, we demonstrate an interesting relationship between the N/C molar ratio and the N content of NDCs. The upper limit for the nitrogen content of NDCs that might be achieved was estimated and found to strongly depend on the carbonization temperature (14.32 wt % at 1000 °C and 21.66 wt % at 900 °C), irrespective of the precursor or preparation conditions. Simulations suggest that, especially in the carbon architectures obtained at high temperatures, nitrogen atoms are always located on separate hexagon moieties in a graphitic configuration, thereby yielding a critical N/C molar ratio very close to the value estimated from the experimental results.     

Strong convergence theorems for nonexpansive mappings and nonexpansive semigroups

In this paper, we show strong convergence theorems for nonexpansive mappings and nonexpansive semigroups in Hilbert spaces by the hybrid method in the mathematical programming.     

Structure of thiotropocin,a new sulfur-containing 7-membered antibiotic

The structure of a new antibiotic thiotropocin is described.     

Radical cyclopolymerizations of diallylsilanes and triallylsilanes

The radical polymerizations of diallylsilanes such as diallyldimethylsilane ( 1 ) and diallylmethylphenylsilane ( 2 ) have been conducted. Both poly(diallyldimethylsilane) ( 3 ) and poly(diallylmethylphenylsilane) ( 4 ) are soluble in benzene, methyl ethyl keton (MEK), and chloroform, slightly soluble in acetone, and insoluble in methanol and ethanol. No insoluble fraction of either polymer was obtained. Very little evidence of vinyl protons in the ¹H-NMR spectra can indicate that both polymerizations predominantly proceed with intramolecular cyclization. In order to study the ring size of cyclic structure in the repeating unit of the polymers, a model compound, allyl(2-chloropropyl)dimethylsilane ( 5 ), was synthesized and cyclized with Bu₃SnH in the presence of azobisisobutyronitrile (AIBN) in benzene, under similar condition of those for the cyclopolymerizations. The product was analyzed with GC–MS which showed that the five-membered ring compound, 1,1,3,4-tetramethylsilacyclopentane, was not formed. From the result of the cyclization of the model compound, it can be suggested that the polymerizations undergo with only h–t intramolecular cyclization to form a six-membered ring in the repeated unit. The ¹³C-NMR spectra of 3 and 4 were measured to study the ring size and the configuration of the cyclic structures. The two peaks at ?1.6 and ?3.4 ppm of the spectrum of 3 show that there are two kinds of methyl carbons in the repeating unit. From consideration of the model reaction and the number of the peaks of the NMR spectrum, it can be considered that the polymer main chain is assembled with the six-membered ring in cis-form, and the two signals are assigned to equatorial and axial methyl carbons, respectively. The two peaks at -1.5 and -5.1 ppm of the ¹³C-NMR spectrum of 4 can be assigned similarly. The radical cyclopolymerizations of triallylsilanes such as methyltriallylsilane ( 6 ) and phenyltriallylsilane ( 7 ) were conducted. The ¹H-NMR spectra of poly(methyltriallylsilane) ( 8 ) and poly(phenyltriallylsilane) ( 9 ) show broad peak around 5 ppm for vinyl protons and around 2 ppm for alkyl protons. Comparisons of the relative intensities of the peaks indicate that both polymerizations undergo with single ring closure to form a polymer with monocyclic structure moiety, cyclosilahexane, and an allyl group in a repeating unit of 8 and 9 .     

Infrared spectroscopy of ozone-water complex in a neon matrix

Matrix isolation infrared spectroscopy has been applied to study an ozone-water complex of atmospheric interest. The complex was identified in the spectral region of three normal modes of ozone and water. Ab initio calculation at MP4(SDQ), QCISD, and CCSD(T) levels indicates the existence of only one stable conformer, which accords with the present experimental result. This conformer belongs to the Cs symmetry group where two molecular planes of ozone and water are perpendicular to the Cs symmetry plane. The binding energy was calculated to be 1.89 kcal/mol at the CCSD(T)/6-311++G(3df,3pd)//CCSD(T)/6-311++G(d,p) level of theory. The formation constant and atmospheric abundance of the ozone-water complex are estimated using the thermodynamic and spectroscopic data obtained.