The effect of methyl substitution on the spin-state in solid bis(methyl-substituted 2-pyridinalphenylimine)di(thiocyanato)iron(II)

Summary A series of iron(II) complexes of the type [FeL₂(NCS)₂] have been prepared and characterized, where L denotes the bidentate diimine ligands 2-pyridinalphenylimine orN-phenyl-2-pyridinaldimine (ppi) and its methyl-substituted derivatives. The electronic ground spin-state of iron(II) in these complexes has been studied by means of Mössbauer spectroscopy and magnetic susceptibility measurements.     

The First Triple‐Stranded Helical Metallosupramolecule with Metal Cluster Core

An unprecedented 3D framework, [Ag(Ag6(C2‐Me‐(Mepdz)₂)₃(CH₃CN))₂](ClO₄)₁₃, has been synthesized by using a ligand with both rigid pyridazine and flexible hydrazone segments, which represents to the best of our knowledge, the first example of metallosupramolecule built by the triple‐stranded helixes sharing the same penta‐silver core.     

tert-BuOK-mediated carbanion-yne intramolecular cyclization: synthesis of 2-substituted 3-benzylbenzofurans

A mild, efficient, and regioselective carbanion-yne intramolecular cyclization mediated by t-BuOK for the synthesis of 2-substituted 3-benzylbenzofurans is developed. It was started from o-iodophenol (1), based on O-alkylation, and the Sonogashira reaction in sequence to produce 2-(2-phenylethynylphenoxy)-1-arylalkanones (5). An intramolecular carbanion-yne 5-exo-dig cyclization reaction of 5, which was mediated by t-BuOK, yielded title benzofurans in good yields.     

Pressure- and heat-induced insertion of CO2 into an auxetic small-pore zeolite

When the small-pore zeolite natrolite is compressed at ca. 1.5 GPa and heated to ca. 110 °C in the presence of CO(2), the unit cell volume of natrolite expands by 6.8% and ca. 12 wt % of CO(2) is contained in the expanded elliptical channels. This CO(2) insertion into natrolite is found to be reversible upon pressure release.     

ToF-SIMS imaging of the nanoscale phase separation in polymeric light emitting diodes: effect of nanostructure on device efficiency

The nanostructure of the light emissive layer (EL) of polymer light emitting diodes (PLEDs) was investigated using force modulation microscopy (FMM) and scanning time-of-flight secondary ion mass spectrometry (ToF-SIMS) excited with focused Bi(3)(2+) primary beam. Three-dimensional nanostructures were reconstructed from high resolution ToF-SIMS images acquired with different C(60)(+) sputtering times. The observed nanostructure is related to the efficiency of the PLED. In poly(9-vinyl-carbazole) (PVK) based EL, a high processing temperature (60 °C) yielded less nanoscale phase separation than a low processing temperature (30 °C). This nanostructure can be further suppressed by replacing the host polymer with poly[oxy(3-(9H-9-carbazol-9-ilmethyl-2-methyltrimethylene)] (SL74) and poly[3-(carbazol-9-ylmethyl)-3-methyloxetane] (RS12), which have similar chemical structures and energy levels as PVK. The device efficiency increases when the phase separation inside the EL is suppressed. While the spontaneous formation of a bicontinuous nanostructure inside the active layer is known to provide a path for charge carrier transportation and to be the key to highly efficient polymeric solar cells, these nanostructures are less efficient for trapping the carrier inside the EL and thus lower the power conversion efficiency of the PLED devices.     

Densities,viscosities, refractive indices,and surface tensions for binary and ternary mixtures of 2-propanol,tetrahydropyran, and 2,2,4-trimethylpentane

Densities, viscosities, refractive indices, and surface tensions of the ternary system (2-propanol + tetrahydropyran + 2,2,4-trimethylpentane) at T = 303.15 K and its constituent binary systems (2-propanol + tetrahydropyran, 2-propanol + 2,2,4-trimethylpentane, and tetrahydropyran + 2,2,4-trimethylpentane) at T = (293.15, 303.15, 313.15, and 323.15) K were measured at atmospheric pressure. Densities were determined using a vibrating-tube densimeter. Viscosities were measured with an automatic microviscometer based on the rolling-ball principle. Refractive indexes were measured using a digital Abbe-type refractometer. Surface tensions were determined by the Wilhelmy-plate method. From these data, excess molar volumes, deviations in viscosity, deviations in refractive index, and deviations in surface tension were calculated. The results for the binary and ternary systems were fitted to the Redlich–Kister equation and the variable-degree polynomials in terms of compositions, respectively. The experimental and calculated quantities are used to study the nature of mixing behaviour between mixture components.     

Off-on-off luminescent switching of a dye containing imidazo[4,5-f][1,10]phenanthroline

A new acid-base fluorescent switch containing both imidazo[4,5-f][1,10]-phenanthroline and triphenylamine groups has been synthesized.Its fluorescence emissions and absorptions can be reversibiy changed through protonation/deprotonation of imidazole and amine moiety by controlling the intramolecular charge transfer(ICT) process,leading to off-on-off fluorescent molecular switching.     

Efficient copper-catalyzed S-vinylation of thiols with vinyl halides

The synthesis of vinyl sulfides through the coupling reaction of thiols with vinyl iodides, bromides, and chlorides is described. The thiols can couple with aryl iodides in the presence of only 0.5 mol % Cu(2)O without the need for an ancillary ligand. In the presence of 5 mol % of Cu(2)O and 10 mol % 1,10-phenanthroline as the ligand, the more challenging alkyl vinyl bromides can also be coupled with thiols, giving the vinyl sulfides in good to excellent yields.     

Efficiency measurement using independent component analysis and data envelopment analysis

Efficiency measurement is an important issue for any firm or organization. Efficiency measurement allows organizations to compare their performance with their competitors’ and then develop corresponding plans to improve performance. Various efficiency measurement tools, such as conventional statistical methods and non-parametric methods, have been successfully developed in the literature. Among these tools, the data envelopment analysis (DEA) approach is one of the most widely discussed. However, problems of discrimination between efficient and inefficient decision-making units also exist in the DEA context (Adler and Yazhemsky, 2010). In this paper, a two-stage approach of integrating independent component analysis (ICA) and data envelopment analysis (DEA) is proposed to overcome this issue. We suggest using ICA first to extract the input variables for generating independent components, then selecting the ICs representing the independent sources of input variables, and finally, inputting the selected ICs as new variables in the DEA model. A simulated dataset and a hospital dataset provided by the Office of Statistics in Taiwan’s Department of Health are used to demonstrate the validity of the proposed two-stage approach. The results show that the proposed method can not only separate performance differences between the DMUs but also improve the discriminatory capability of the DEA’s efficiency measurement.     

Toward a four-toothed molecular bevel gear with C2-symmetrical rotors

The design, synthesis, conformational analysis, and variable-temperature NMR studies of pentiptycene-based molecular gears Pp(2)X, where Pp is the unlabeled (in 1H) or methoxy groups-labeled (in 1OM) pentiptycene rotor and X is the phenylene stator containing ortho-bridged ethynylene axles, are reported. The approach of using shape-persistent rotors of four teeth but C(2) symmetry for constructing four-toothed molecular gears is unprecedented. In addition, the first example of enantioresolution of chiral pentiptycene scaffolds is demonstrated. Density functional theory (DFT) and AM1 calculations on these Pp(2)X systems suggest two possible correlated torsional motions, geared rocking and four-toothed geared rotations, which compete with the uncorrelated gear slippage. The DFT-derived torsional barriers in 1H for rocking, four-toothed rotation, and gear slippage are approximately 2.9, 5.5, and 4.7 kcal mol(-1), respectively. The low energy barriers for these torsional motions result from the low energy cost of bending the ethynylene axles. Comparison of the NMR spectra of 1OM in a mixture of stereoisomers (1OM-mix) and in an enantiopure form (1OM-op) confirms a fast gear slippage in these Pp(2)X systems. The effect of the methoxy labels on rotational potential energy surface and inter-rotor dynamics is also discussed.