Induction of molecular chirality by circularly polarized light in cyclic azobenzene with a photoswitchable benzene rotor

New phototriggered molecular machines based on cyclic azobenzene were synthesized in which a 2,5‐dimethoxy, 2,5‐dimethyl, 2,5‐difluorine or unsubstituted‐1,4‐dioxybenzene rotating unit and a photoisomerizable 3,3′‐dioxyazobenzene moiety are bridged together by fixed bismethylene spacers. Depending upon substitution on the benzene moiety and on the E/Z conformation of the azobenzene unit, these molecules suffer various degrees of restriction on the free rotation of the benzene rotor. The rotation of the substituted benzene rotor within the cyclic azobenzene cavity imparts planar chirality to the molecules. Cyclic azobenzene 1 , with methoxy groups at both the 2‐ and 5‐positions of the benzene rotor, was so conformationally restricted that free rotation of the rotor was prevented in both the E and Z isomers and the respective planar chiral enantiomers were resolved. In contrast, compound 2 , with 2,5‐dimethylbenzene as the rotor, demonstrated the property of a light‐controlled molecular brake, whereby rotation of the 2,5‐dimethylbenzene moiety is completely stopped in the E isomer (brake ON, rotation OFF), while the rotation is allowed in the Z isomer (brake OFF, rotation ON). The cyclic azobenzene 3 , with fluorine substitution on the benzene rotor, was in the brake OFF state regardless of E/Z photoisomerization of the azobenzene moiety. More interestingly, for the first time, we demonstrated the induction of molecular chirality in a simple monocyclic azobenzene by circular‐polarized light. The key characteristics of cyclic azobenzene 2 , that is, stability of the chiral structure in the E isomer, fast racemization in the Z isomer, and the circular dichroism of enantiomers of both E and Z isomers, resulted in a simple reversible enantio‐differentiating photoisomerization directly between the E enantiomers. Upon exposure to r‐ or l‐circularly polarized light at 488 nm, partial enrichment of the (S)‐ or (R)‐enantiomers of 2 was observed.     

Weak ferromagnetism and strong spin-spin interaction mediated by the mixed-valence ethynyltetrathiafulvalene-type ligand

A new chromium complex with ethynyltetrathiafulvalene (TTF)-type ligands, [CrCyclam(C≡C-5-methyl-4'5'-ethylenedithio-TTF)(2)]OTf ([1]OTf), was synthesized. The cyclic voltammetry of the complex shows two reversible oxidation waves owing to the first and second oxidation of the TTF unit. The electrochemical oxidation of [1]OTf in a Bu(4)NClO(4) or Bu(4)NBF(4) solution of a 1:1 acetonitrile-chlorobenzene mixture gave isostructural crystals of [1][ClO(4)](2)(PhCl)(2)(MeCN) and [1][BF(4)](2)(PhCl)(2)(MeCN), where two mixed-valence TTF units of adjacent complexes form a dimer radical cation. The crystal structures are characterized by an alternating chain of S = 3/2 Cr(3+)Cyclam units and S = ? (TTF)(2)(+) dimers. These two paramagnetic components are connected directly by an ethynyl group, resulting in a strong intrachain spin-spin interaction of 2J/k(B) = -30 and -28 K for [ClO(4)](-) and [BF(4)](-) salts, respectively (H = -2J∑(i)S(i)·S(i+1)). Both salts show a weak ferromagnetic transition at 23 K thanks to interchain antiferromagnetic interaction between TTF dimers. The remanent magnetizations and coercive forces of nonoriented samples at 1.8 K are 0.016 μ(B) and 90 mT for the [ClO(4)](-) salt and 0.010 μ(B) and 50 mT Oe for the [BF(4)](-) salt, respectively. The weak ferromagnetism is attributed to the Dzyaloshinsky-Moriya interaction between adjacent TTF dimers and/or the single-ion anisotropy of [1](2+).     

Thermo‐Responsive Hydrogels with Nanodomains: Rapid Shrinking of a Nanogel‐Crosslinking Hydrogel of Poly(N‐isopropyl acrylamide)

Rapidly shrinking poly(N‐isopropyl acrylamide) (PNIPAM) hydrogels are prepared by crosslinking with self‐assembled nanogels that consist of cholesteryl‐ and methacryloyl‐substituted pullulan (CHPMA). The CHPMA nanogel (R_h = 26.4 nm) was used as a crosslinker for a hydrophilic nanodomain. Transmission electron microscopy images of the nanogel‐crosslinked PNIPAM hydrogel reveal a well‐defined nanoporous structure. The nanogel‐crosslinked PNIPAM hydrogel shows rapid shrinking based on its structure. The shrinking half‐time was ≈2 min, which is about 3 400 times faster than that of a PNIPAM hydrogel crosslinked by methylene(bisacrylamide).

     

Evidence for strong Breit interaction in dielectronic recombination of highly charged heavy ions

Resonant strengths have been measured for dielectronic recombination of Li-like iodine, holmium, and bismuth using an electron beam ion trap. By observing the atomic number dependence of the state-resolved resonant strength, clear experimental evidence has been obtained that the importance of the generalized Breit interaction (GBI) effect on dielectronic recombination increases as the atomic number increases. In particular, it has been shown that the GBI effect is exceptionally strong for the recombination through the resonant state [1s2s(2)2p(1/2)](1).     

Generation of high-fidelity four-photon cluster state and quantum-domain demonstration of one-way quantum computing

We experimentally demonstrate a simple scheme for generating a four-photon entangled cluster state with fidelity over 0.860+/-0.015. We show that the fidelity is high enough to guarantee that the produced state is distinguished from Greenberger-Horne-Zeilinger, W, and Dicke types of genuine four-qubit entanglement. We also demonstrate basic operations of one-way quantum computing using the produced state and show that the output state fidelities surpass classical bounds, which indicates that the entanglement in the produced state essentially contributes to the quantum operation.     

Gravitational Effects on Mixing and Growth Morphology of an In0.5Ga0.5 System

A mixing experiment of multicomponents melts was performed using a uniform temperature furnace in the Second International Microgravity Laboratories (IML-2) mission. Growth morphologies and Ga concentration profiles were analyzed for the samples with the compositional ratio of 0.5 In–0.5 Ga–1.0 Sb grown under microgravity and on earth. The sample with free surface grown under microgravity was nearly spherical in shape, except some parts with projections. Ga was dispersed homogeneously in the bulk because the mixing was enhanced by Marangoni convection due to the concentration gradient. On the other hand, the sample grown on earth was a double cylindrical shape with different diameters, and Ga concentration decreased from top to bottom, showing clearly the effect of gravity. Many needle crystals were formed in both space and earth samples due to rapid cooling. The average size of the needle crystals grown in space was larger than that of the earth sample.     

An Inverse Problem of Determining Coefficients in a One-Dimensional Radiative Transport Equation

We consider an inverse problem of determining unknown coefficients for a one-dimensional analogue of radiative transport equation. We show that some combination of the unknown coefficients can be uniquely determined by giving pulse-like inputs at the boundary and observing the corresponding outputs. Our result can be applied for determination of absorption and scattering properties of an optically turbid medium if the radiative transport equation is appropriate for describing the propagation of light in the medium.