Studies of heteroaromaticity—LXVI: Photochemical and thermal behaviours of heterocycles involving azido-ketone moiety

The photolyses and thermolyses of compounds 1 and 2 in a nucleophilic solvent such as alcohol and diethylamine have been studied and form 4,5-disubstituted amino and alkoxy or dialkylamino groups. The mechanism for the formation of the products are proposed and discussed.     

Molecular structures of endo[4+2]π and exo[6+4]π cycloadducts via cycloaddition reaction of n-ethoxycarbonylazepine with 2,5-dimethoxycarbonyl-3,4-diphenylcyclopentadienone

The cycloaddition reaction of N-ethoxycarbonyl-1H-azepine with 2,5-dimethoxycarbonyl-3,4-diphenylcyclopentadienone gave anti-endo [4+2]π and exo [6+4]π cycloadducts. These structures were fully identified by X-ray crystallographic techniques. Mechanism for their cycloaddition reactions are also discussed.     

Low‐Symmetry Ω‐Shaped Zinc Phthalocyanine Sensitizers with Panchromatic Light‐Harvesting Properties for Dye‐Sensitized Solar Cells

Two low‐symmetry phthalocyanines (Pcs) substituted with thiophene units at the non‐peripheral (α) and peripheral (β) positions were synthesized and their optical, electronic‐structure, and electrochemical properties were investigated. The substitution of thiophene units at the α positions of the phthalocyanine skeleton resulted in a red shift of the Q band and significantly modified the molecular‐orbital electronic distributions just below the HOMO and just above the LUMO, with distortion of the typical Gouterman four‐orbital arrangement of MOs. Two amphiphilic Ω‐shaped ZnPcs ( αPcS1 and αPcS2 ) bearing a π‐conjugated side chain with an adsorption site at an α position of the Pc macrocycle were synthesized as sensitizers for dye‐sensitized solar cells (DSSCs). The absorption spectra of αPcS1 and αPcS2 showed red shifted Q bands and a broad band from 350 to 550 nm assignable to the intramolecular charge‐transfer transition from the ZnPc core to the side chains. Time‐dependent DFT calculations provided a clear interpretation of the effect of the thiophene conjugation on the typical phthalocyanine core π MOs. Compound αPcS1 was used as a light‐harvesting dye on a TiO₂ electrode for a DSSC, which showed a panchromatic response in the range 400–800 nm with a power conversion efficiency of 5.5 % under one‐sun conditions.     

Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

Effect of the Ethanol/BTC Ratio on the Methane Uptake of Mechanochemically Synthesized MOF-199

We report on a detailed textural analysis of mechanochemically synthesized MOF-199 including N₂ adsorption-desorption and CO₂ adsorption isotherms data at 77 K and 273 K (up to atmospheric pressure), respectively, and CH₄ adsorption data at 298 K (up to 35 bar). We used the isotherm adsorption data to determine the micropore volume of the MOF-199 structures, to establish their methane uptake capacity and to understand how these properties depended on the Ethanol/BTC ratio used during the synthesis. The maximum methane uptake capacity for our specimens was recorded at 130 v/v at 35 bars. These results open an avenue for a better understanding of alternative manufacturing processes of MOF structures for gas storage applications.     

Stacking Control by Molecular Symmetry of Sterically Protected Phthalocyanines

The synthesis and characterization of two phthalocyanine (Pc) structural isomers, 1 and 2, in which four 2,6-di(hexyloxy)phenyl units were attached directly to the 1,8,15,22- or 1,4,15,18-positions of the Pc rings, are described. Both Pcs 1 and 2 exhibited low melting points, i.e., 120 and 130 °C respectively, due to the reduction in intermolecular π-π interaction among the Pc rings caused by the steric hindrance of 2,6-dihexyloxybenzene units. The thermal behaviors were investigated with temperature-controlled polarizing optical microscopy, differential scanning calorimetry, powder X-ray diffraction, and absorption spectral analyses. Pc 1, having C_4h molecular symmetry, organized into a lamellar structure containing lateral assemblies of Pc rings. In contrast, the other Pc 2 revealed the formation of metastable crystalline phases, including disordered stacks of Pcs due to rapid cooling from a melted liquid.     

Novel family of low molecular weight hydrogelators based on L-lysine derivatives

New L-lysine derivatives with a positively charged terminal can gel water below 1 wt%; particularly, 1a and 2a form a hydrogel at 0.3 wt% corresponding to approximately 12,300 and 12,500 waters/gelator molecule, respectively.     

Hypergeometric Polynomials and Integer Programming

We examine connections between A-hypergeometric differential equations and the theory of integer programming. In the first part, we develop a hypergeometric sensitivity analysis for small variations of constraint constants with creation operators and b-functions. In the second part, we study the indicial polynomial (b-function) along the hyperplane xi=0 via a correspondence between the optimal value of an integer programming problem and the roots of the indicial polynomial. Gröbner bases are used to prove theorems and give counter examples.     

Statistical analysis of fluctuations of froth pressure on perforated plates without downcomers

Statistical properties of fluctuations of pressure drop across the gas–liquid dispersions on the tray were analyzed using a 215 mm dia. three plates column with different trays. Hydrodynamic regimes of the froth were characterized in terms of the statistical properties evaluated. It was proved that the on-line estimation of the flow behavior of the froth was possible on the basis of the pattern recognition of the power spectral density function of the pressure fluctuations. The time-domain stochastic models for fluctuations of the pressure drop were identified so as to be available for its forecast and simulation.