Living ethylene/norbornene copolymerisation catalyzed by titanium complexes having two pyrrolide-imine chelate ligands

Ethylene/norbornene copolymerisation behaviour of titanium complexes with two pyrrolide-imine chelate ligands is described.     

A general and straightforward route toward diarylmethanes. Integrated cross-coupling reactions using (2-pyridyl)silylmethylstannane as an air-stable,storable, and versatile coupling platform

[reaction: see text] Pharmacologically important diarylmethane structures have been prepared in a straightforward manner through sequentially integrated Pd-catalyzed cross-coupling reactions. (2-Pyridyl)silylmethylstannane was found to be an air-stable, storable, and versatile coupling platform in this synthetic strategy.     

Charge separation in a novel artificial photosynthetic reaction center lives 380 ms.

An extremely long-lived charge-separated state has been achieved successfully using a ferrocene-zincporphyrin-freebaseporphyrin-fullerene tetrad which reveals a cascade of photoinduced energy transfer and multistep electron transfer within a molecule in frozen media as well as in solutions. The lifetime of the resulting charge-separated state (i.e., ferricenium ion-C(60) radical anion pair) in a frozen benzonitrile is determined as 0.38 s, which is more than one order of magnitude longer than any other intramolecular charge recombination processes of synthetic systems, and is comparable to that observed for the bacterial photosynthetic reaction center. Such an extremely long lifetime of the tetrad system has been well correlated with the charge-separated lifetimes of two homologous series of porphyrin-fullerene dyad and triad systems.     

Enantioselective total synthesis of a potent antitumor antibiotic, fredericamycin A.

The asymmetric total synthesis of both enantiomers of the potent antitumor antibiotic fredericamycin A (1) is detailed based on the protocol for the construction of its peri-hydroxy polyaromatic skeleton bearing the chirality at the spiro carbon via a strong base-induced cycloaddition of suitably substituted homophthalic anhydrides (AB-ring unit) with an optically active CDEF-ring unit. Particular attention has been given to the novel synthesis of the optically active spiro carbon center by a stereospecific rearrangement of optically active benzofuzed-trans-epoxy acylates leading to spirocyclopentane-1,1'-indane systems. This method is quite useful for the construction of an optically active spiro compound and was applied to the synthesis of the optically pure CDEF-ring unit of 1. Cycloaddition of the optically pure CDEF-ring unit to AB-ring units prepared via benzyne afforded two natural and unnatural-type hexacyclic compounds, which were converted to natural and unnatural enantiomers of synthetic 1, and the absolute configuration of natural 1 was determined as S.     

Phase Transition Behaviors of Self‐Oscillating Polymer and Nano‐Gel Particles

Summary: Self‐oscillating polymers and nano‐gel particles consisting of N‐isopropylacrylamide and the ruthenium catalyst of the Belousov‐Zhabotinsky reaction have been prepared. In order to clarify the crosslinking effect on the self‐oscillating behavior, the phase transition behaviors were investigated by measuring the transmittance and the fluorescence intensity of the polymer solution and the gel bead suspension. Cooperative effects due to crosslinking will play an important role for the design of nanoactuators.

Chemical structure of poly(NIPAAm‐co‐Ru(bpy)₃).     

Epstein–Penner Decompositions and Thrice Punctured Spheres in Hyperbolic 3-Manifolds

Let M be a cusped hyperbolic 3-manifold containing an incompressible thrice punctured sphere S. Suppose that M is not the Whitehead link complement. We prove that a certain arc on S is isotopic to an edge of a Euclidean decomposition of M. By using the above result, we relate alternating knot diagrams and the canonical decompositions. Let K be an alternating hyperbolic knot. On a reduced alternating knot diagram of K, if we replace one of the crossings with a large number of half twists, the polar axis of the crossing is isotopic to an edge of the canonical decomposition for the resulting knot.     

Study of S11 resonance in nuclei through (γ, η) reactions

In order to study the S₁₁(1535) resonance in the nuclear medium, total cross sections of the (γ, η) reactions on C, Al and Cu have been measured for photon energies between 680 and 1000 MeV. A broad resonance due to the excitation and decay of the S₁₁ resonance in the nucleus has been clearly observed for the first time. The apparent energy and width of the resonance are 900 and 300 MeV, respectively. Model calculations based on the quantum molecular dynamics have been performed. A comparison of the calculations with the data indicates that the S₁₁ resonance in nuclei should have a larger width; the width of about 250 MeV is required while the elementary one is about 150 MeV.     

Robust Triplatinum Redox-Chromophore for a Post-Synthetic Color-Tunable Electrochromic System

An electrochromic system showing ease of color tunability has been constructed using a triple-decker Pt^II complex [Pt₃(μ₃-pydt)₂(bpy)₃]²⁺ (H₂pydt=2,6-pyridinedithiol, bpy=2,2′-bipyridine). The divalent complex undergoes electrochemically quasi-reversible two-electron transfer coupled with the coordination/dissociation of axial ligands, forming higher valent Pt(+2.67) species [Pt₃X₂(μ₃-pydt)₂(bpy)₃]²⁺ (X=Cl⁻, Br⁻, and SCN⁻). These higher valent species exhibit characteristic colors ranging from red to cyan depending on the counter anion X⁻ of the electrolyte. The triple-decker structure provides a novel multicolor electrochromic system with favorable stability and reversibility. Theoretical calculations indicate that the colors of the Pt(+2.67) species are tunable by the trans influence of the axial ligand X⁻. This novel strategy of post-synthetic color-tuning using triplatinum systems should enable the facile preparation of colorful electrochromic devices without any complicated procedures, which may find application in flexible displays, optical devices, and sensors.