1,2,3-Triazol-5-ylidene-palladium complex catalyzed Mizoroki-Heck and Sonogashira coupling reactions

The bis-1,4-dimesityl-1,2,3-triazol-5-ylidene-palladium complex (1a) successfully catalyzes the Mizoroki-Heck and Sonogashira coupling reactions with aryl bromides to give the corresponding alkenes and alkynes, respectively, in good to excellent yields. In the Mizoroki-Heck reaction, electron-rich, electron-poor, and functionalized aryl bromides and alkenes are tolerated, while the substrates are limited to electron-poor aryl halides in the Sonogashira coupling reaction. The palladium complex also catalyzes cross-coupling reactions with aryl chlorides to give higher yields of products than does the bis-IMes-Pd complex analogue (2), under specific conditions.     

Vibrational properties of CaAlH5 and α-AlH3 with different AlH6 networks studied by inelastic neutron scattering

We performed a combined study using inelastic neutron scattering (INS) and first-principles calculations of the vibrational properties of CaAlH(5) and α-AlH(3) with different AlH(6) networks, a zigzag one-dimensional AlH(6) network for CaAlH(5), and a three-dimensional AlH(6) network for α-AlH(3). Both materials showed qualitatively similar INS spectra, in which CaAlH(5)/α-AlH(3) was mainly divided into three regions: (i) the translational modes (318/316 cm(-1)), (ii) the librational modes of the octahedral AlH(6) units (external molecular motion) in the lower frequency range and H-Al-H bond-bending modes (intra molecular motion) at a higher frequency (420-1157/513-1038 cm(-1)), and (iii) the Al-H bond-stretching modes (1238-1750/1486-1942 cm(-1)). In region ii, the appearance of both librational and bond-bending modes was determined by the networked nature of the octahedral AlH(6) units. In addition, the librational modes of AlH(6) on α-AlH(3) exhibit higher frequencies than CaAlH(5) due to the tighter bonding between the octahedral AlH(6) units. With regard to average frequencies for the Al-H, ω(S), bond-stretching modes, and average Al-H bond distances on the aluminum-based hydrides including CaAlH(5) and α-AlH(3), ω(S) showed lower frequencies that correlate with lengthening of the Al-H bond distances.     

Phase-matched Raman-resonant four-wave mixing in a dispersion-compensated high-finesse optical cavity

A highly efficient intracavity four-wave mixing in a Raman-active medium pumped by a continuous-wave laser is first demonstrated. Managing the intracavity dispersion to satisfy the phase matching in a high-finesse cavity substantially enhances the anti-Stokes emission. This process is observed in a region far beyond small signal approximation, indicating the generation of phase-locked sidebands arising from molecular modulation. This points to a novel approach of an optical modulator and mode-locked laser operating at a frequency of more than 10 THz.     

How Does Pressure Fluctuate in Equilibrium?

We study fluctuations of pressure in equilibrium for classical particle systems. In equilibrium statistical mechanics, pressure for a microscopic state is defined by the derivative of a thermodynamic function or, more mechanically, through the momentum current. We show that although the two expectation values converge to the same equilibrium value in the thermodynamic limit, the variance of the mechanical pressure is in general greater than that of the pressure defined through the thermodynamic relation. We also present a condition for experimentally detecting the difference between them in an idealized measurement of momentum transfer.     

The Most Effective Model for Describing the Universal Behavior of a Noisy Kuramoto–Sivashinsky Equation as a Paradigmatic Model

We study a noisy Kuramoto–Sivashinsky (KS) equation which describes unstable surface growth and chemical turbulence. It has been conjectured that the universal long-wavelength behavior of the equation, which is characterized by scale-dependent parameters, is described by a Kardar–Parisi–Zhang (KPZ) equation. We consider this conjecture by analyzing a renormalization-group equation for a class of generalized KPZ equations. We then uniquely determine the parameter values of the KPZ equation that most effectively describes the universal long-wavelength behavior of the noisy KS equation.     

New methodology for synthesizing polyolefinic graft block copolymers and their morphological features

This paper describes a new synthetic route for polyolefinic graft block copolymers by adopting coupling reaction between terminally hydroxylated polyolefins and maleic anhydride grafted polyolefins. Terminally hydroxylated polypropylene (PP-OH) was coupled with maleic anhydride modified polyethylene (PE-g-MAH) and such ethylene-propylene random copolymer (EPR-g-MAH) to give polyolefinic graft block copolymers (PE-g-PP and EPR-g-PP, respectively). The formation of PE-g-PP was confirmed by enhancement on molecular weight and it brought about distinctive decrease in size of dispersed domain in its phase separation morphology. Occurrence of coupling reaction to give EPR-g-PP was indicated by extreme decrease in its solubility to n-decane and it led to unique morphology demonstrating lamella microstructure that had never been reported for a comparable polyolefin composite.     

Polymacromonomers with polyolefin branches synthesized by free-radical homopolymerization of polyolefin macromonomer with a methacryloyl end group

Polymacromonomers with polyolefin branches were successfully synthesized by free-radical homopolymerization of polyolefin macromonomer with a methacryloyl end group. Propylene-ethylene random copolymer (PER) with a vinylidene end group was prepared by polymerization using a metallocene catalyst. Then, the unsaturated end group was converted to a hydroxy end group via hydroalumination and oxidation. The PER with the hydroxy end group was easily reacted with methacryloyl chloride to produce methacryloyl-terminated PER (PER macromonomer; PERM). The free-radical polymerization of thus-obtained PERM was done using 2,2′-azobis(isobutyronitorile) (AIBN) as a free-radical initiator. From NMR analyses, the obtained polymers were identified as poly(PERM). Based on gel permeation chromatography (GPC), the estimated degree of polymerization (D_p) of these polymers were about 30. Thus, new class of polymacromonomers with polyolefin branches was synthesized.     

Free radical polymerization within mesoporous zeolite channels

Free radical polymerization of methyl methacrylate (MMA) within the uniform channels of the mesoporous zeolite MCM-41 proceeds at 100°C to give a high molecular weight polymer (PMMA). The formation of long-living propagating polymer-radicals is observed by electron paramagnetic resonance (EPR). The molecular weight of PMMA within the mesopores can be controlled over a wide range by changing the monomer-to-initiator mole ratio.     

Unveiling ultrafast dynamics in bridged bimetallic complexes using optical and X-ray transient absorption spectroscopies

In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. Here, we use ultrafast optical and X-ray spectroscopies to elucidate the effects of metal–metal interactions in a bimetallic tetrapyridophenazine-bridged Os(ii)/Cu(i) complex. Despite having an appropriate driving force for Os-to-Cu hole transfer in the Os(ii) moiety excited state, no such charge transfer was observed. However, excited-state coupling between the metal centers is present, evidenced by variations in the Os MLCT lifetime depending on the identity of the opposite metal center. This coupling results in concerted coherent vibrations appearing in the relaxation kinetics of the MLCT states for both Cu and Os centers. These vibrations are dominated by metal–ligand contraction at the Cu/Os centers, which are in-phase and linked through the conjugated bridging ligand. This study shows how vibronic coupling between transition metal centers affects the ultrafast dynamics in bridged, multi-metallic systems from the earliest times after photoexcitation to excited-state decay, presenting avenues for tuning charge-transfer states through judicious choice of metal/ligand groups.

In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers.     

Characterizing the universal rigidity of generic tensegrities

Mathematical Programming - A tensegrity is a structure made from cables, struts, and stiff bars. A d-dimensional tensegrity is universally rigid if it is rigid in any dimension $$d'$$ with...