A Multi‐Addressable Switch Based on the Dimethyldihydropyrene Photochrome with Remarkable Proton‐Triggered Photo‐opening Efficiency

A series of photochromic derivatives based on the trans‐10b,10c‐dimethyl‐10b,10c‐dihydropyrene (DHP, “closed form”) skeleton has been synthesized and their photoisomerization leading to the corresponding cyclophanediene (CPD, “open form”) isomers has been investigated by UV/Vis and ¹H NMR spectroscopies. Substitution of the DHP core with electron‐withdrawing pyridinium groups was found to have major effects on the photoisomerization efficiency, the most remarkable examples being to enhance the quantum yield of the opening reaction and to allow fast and quantitative conversions at much lower radiant energies. This effect was rationalized by theoretical calculations. We also show that the reverse reaction, that is, going from the open form to the closed form, can be electrochemically triggered by oxidation of the CPD unit and that the photo‐opening properties of pyridine‐substituted DHPs can be efficiently tuned by protonation, the system behaving as a multi‐addressable molecular switch. These multi‐addressable photochromes show promise for the development of responsive materials.     

Towards the limit of atropochiral stability: H-MIOP, an N-heterocyclic carbene precursor and cationic analogue of the H-MOP ligand

The configurational stability of biaryl motifs is addressed for the 1-naphthyl-N-benzimidazolyl motif substituted by a single diphenylphosphinyl group at the 2-position. The atropoenantiomers of the N-methylated cation H-MIOP, a less sterically locked analogue of the neutral H-MOP ligand, were resolved by enantiospecific cleavage of the N(2)C-P bond of the resolved enantiomers of BIMIONAP. The latter were obtained by enantiospecific N-methylation of the previously resolved enantiomers of neutral BIMINAP. PdCl(2) complexes of the P,C-chelating N-heterocyclic carbene (NHC)-phosphine ligands derived from (R)- and (S)-H-MIOP were prepared by two enantiospecific routes: by N(2)C-P bond cleavage from the (R)- and (S)-BIMIONAP-PdCl(2) complexes, or by simultaneous coordination of the P and C atoms of the in situ generated free NHC-phosphine. The enantiomerization pathways of H-MOP, H-MIOP, and corresponding NHC-phosphine have been investigated at the B3PW91/6-31G(d,p) level of theory. The calculated enantiomerization barriers of H-MOP and H-MIOP in acetonitrile are equal to 176.0 and 146.4 kJ mol(-1), respectively, and are mainly determined by the distortion of the naphthalene and/or benzimidazole motifs in the transition state. Beyond the stability of their optical rotation at room temperature, the respective calculated Oki's racemization temperatures of 334 and 225 °C allowed us to consider both ligands as configurationally stable.     

Yukawa potentials in systems with partial periodic boundary conditions. II. Lekner sums for quasi-two-dimensional systems

Yukawa potentials may be long-ranged when the Debye screening length is large. In computer simulations, such long-ranged potentials have to be taken into account with convenient algorithms to avoid systematic bias in the sampling of the phase space. Recently, we provided Ewald sums for quasi-two-dimensional systems with Yukawa interaction potentials [J. Chem. Phys. 126, 056101 (2007); Molec. Phys. paper I of this series]. Sometimes, Lekner sums are used as an alternative to Ewald sums for Coulomb systems. In the present work, we derive the Lekner sums for quasi-two-dimensional systems with Yukawa interaction potentials and we give numerical tests for practical implementations. The main result of this paper is to emphasize that Lekner sums cannot be considered as an alternative to Ewald sums for Yukawa potentials. As a conclusion to this work: Lekner sums should not be used for quasi-two-dimensional systems with Yukawa interaction potentials.     

EELS measurements of boron concentration profiles in p-a-Si and nip a-Si solar cells

The p-type Si layer in a-Si and μc-Si solar cells on foil needs to fulfil several important requirements. The layer is necessary to create the electric field that separates the photo-generated charge carriers; the doping also increases the conductivity to conduct the photocurrent to the front contact; on the other hand, the p-layer should transmit the incident light efficiently to the intrinsic absorber layer. We show that it is possible to study TEM samples prepared, for analysis of possible layer defects, by focussed ion beam milling to detect boron and carbon concentrations as low as 10²⁰ cm^-3, using core-loss EELS combined with numerical analysis. We control the band gap and activation energy of p-a-SiC by varying the B₂H₆ and CH₄ flow during deposition in the process chamber. We have found a linear relation between the activation energy of the dark conductivity E_act and the optical band gap E₀₄. Modelling shows that the optimum efficiency in nip solar cells is obtained when the p-a-SiC band gap is slightly larger than the band gap of the absorber layer. We have assessed the potential of core-loss EELS for detecting B and C concentrations as low as 10²⁰ cm^-3 in a spatially resolved manner, and of low-loss EELS as a probe of the local variations in plasmon energy.     

A unified theory for coherent systems in reliability part III: Two special cases for multinary systems—binary-type coherence and homogeneous coherence

As shown in a companion-paper,¹ binary and multinary coherent systems can be studied with unified arguments, through monotone binary coherent systems. These are binary coherent systems submitted to some monotone constraint and generalize the classic theory of free binary coherent systems. By considering the unified point of view thus obtained, this paper gives what is perhaps the most suggestive representation for multinary coherent systems, since this extends the definition of binary coherent systems in terms of series-parallel (parallel-series) structures. Then, this paper examines the special case of multinary systems that can be studied directly with the classic theory of free binary coherent systems. It thus enlarges and complements, in a shorter unified manner, the particular cases considered in earlier studies.     

Crystal structure and photochemical behavior in solution of the 3'-N-sulfamate analogue of thymidylyl(3'-5')thymidine

The 3'-N-sulfamate analogue of thymidylyl(3'-5')thymidine (TnsoT, 1) exhibits a preference for a C3'-endo conformation in the solution and solid states. Its photochemical behavior in solution is compared to that of its natural counterpart, thymidylyl(3'-5')thymidine (TpT, 2), to get further insight into the significance of the C3'-endo conformation on the photoproduct formation at the single-stranded dinucleotide level. Irradiation at 254 nm of 1 led to the same type of photoproducts as observed with 2. However, 1 was significantly more photoreactive than 2, and accordingly, the initial rate of photoproduct formation was enhanced in accordance with its propensity to base stack compared to 2. The corresponding quantum yields were determined and showed that the enhancement factor (1 compared to 2) is moderate for the cyclobutane pyrimidine dimer (CPD) (1.26) and much higher for the (6-4) photoproduct (1.8). These data strongly suggest that the CPD and (6-4) photoproduct arise from distinct minor stacked conformations.     

Long-chain alkanoic acid esters of lupeol from Dorstenia harmsiana Engl. (Moraceae)

In addition to lupeol (1a), three long-chain alkanoic acid esters of lupeol, in which two were new, were isolated from the hexane and ethyl acetate twigs extract of Dorstenia harmsiana Engl. (Moraceae). The structures of the new compounds were elucidated on the basis of 1D and 2D NMR experiments. Some isolated compounds were evaluated for their antimicrobial activities. The lupeol and its three long-chain alkanoic acid esters showed antifungal and antibacterial activities.