Divergent synthesis of withasomnines via synthesis of 4-hydroxy-1H-pyrazoles and Claisen rearrangement of their 4-O-allylethers

4-Hydroxypyrazoles were synthesized by the alkaline hydrolysis of the Baeyer-Villiger oxidation products of 4-formylpyrazoles. This new synthesis of 4-hydroxypyrazoles was applied to the divergent synthesis of withasomnine alkaloids in a unique strategy, for which the key steps included the regioselective Claisen rearrangement of their 4-O-allyl-4-hydroxy-1H-pyrazoles and a Suzuki coupling of 4-trifluoromethanesulfonyloxy-1H-pyrazoles and arylboronic acids.     

First isolation of fully delocalized mixed-valent imido-bridged [Ti2]7+ complexes by one-electron reduction of [(C5R5)TiCl]2(μ-NAr)2

Mixed-valent imido-bridged dinuclear titanium complexes, [Cp(2)Co][{(C(5)R(5))TiCl}(2)(μ-NAr)(2)] (R = H, Me; Ar = 3,5-(CF(3))(2)C(6)H(3)), were prepared by one-electron reduction of the corresponding [(C(5)R(5))TiCl](2)(μ-NAr)(2). One unpaired electron is delocalized in the central Ti(μ-NR)(2)Ti core as the first example of a fully delocalized mixed-valent imido-bridged [Ti(2)](7+) species.     

Conformational relaxation dynamics of a poly(N-isopropylacrylamide) aqueous solution measured using the laser temperature jump transient grating method

We observed phase transition and phase relaxation processes of a poly(N-isopropylacrylamide) (PNIPAM) aqueous solution using the heterodyne transient grating (HD-TG) method combined with the laser temperature jump technique. The sample temperature was instantaneously raised by about 1.0 K after irradiation of a pump pulse to crystal violet (CV) molecules for heating, and the phase transition was induced for the sample with an initial temperature just below the lower critical solution temperature (LCST); the following phase relaxation dynamics was observed. Turbidity relaxation was observed in both the turbidity and HD-TG responses, while another relaxation process was observed only in the HD-TG response, namely via the refractive index change. It is suggested that this response is due to formation of globule molecules or their assemblies since they would have nothing to do with turbidity change but would affect the refractive index, which is dependent on the molar volume of a chemical species. Furthermore, the grating spacing dependence of the HD-TG responses suggests that the response was caused by the counter propagating diffusion of the coil molecules as a reactant species and the globule molecules as a product species and the lifetime of the globule molecules ranged from 1.5 to 5 seconds. Thus, we conclude that the turbidity reflects the dynamics of aggregate conditions, not molecular conditions. The coil and globule sizes were estimated from the obtained diffusion coefficient. The sizes of the coil molecules did not change at the initial temperatures below the LCST but increased sharply as it approaches LCST. We propose that the coil-state molecules associate due to hydrophobic interaction when the initial temperature was higher than LCST minus 0.5 K and that the globule-state molecules generated from the coil-state molecules showed a similar trend in temperature. The phase transition was also induced by heating under a microscope, and the relaxation process was followed using the fluorescence peak shift of a fluorescent molecule-labeled PNIPAM. The result also supports the existence of a globule molecule or its assembly remains for several seconds in the phase relaxation.     

Alkyne-coordinating tridentate ligands: structural properties and reactivity of their rhodium complexes

Complexes of novel alkyne-chelating tridentate ligands bound to a rhodium atom were isolated and characterised. The present alkyne-rhodium complex underwent dimerisation simply by heating to afford the unprecedented cyclobutadiene dirhodium complex. It is also found that the ligands at the trans positions influence the π-coordination of alkynes.     

Existence of a ground state and scattering for a nonlinear Schrödinger equation with critical growth

We study the energy-critical focusing nonlinear Schrödinger equation with an energy-subcritical perturbation. We show the existence of a ground state in the four or higher dimensions. Moreover, we give a sufficient and necessary condition for a solution to scatter, in the spirit of Kenig and Merle (Invent Math 166:645–675, 2006).     

Naphtho[2,1-b:6,5-b']difuran: a versatile motif available for solution-processed single-crystal organic field-effect transistors with high hole mobility

We here report naphtho[2,1-b:6,5-b']difuran derivatives as new p-type semiconductors that achieve hole mobilities of up to 3.6 cm(2) V(-1) s(-1) along with high I(on)/I(off) ratios in solution-processed single-crystal organic field-effect transistors. These features originate from the dense crystal packing and the resulting large intermolecular π-orbital overlap as well as from the small reorganization energy, all of which originate from the small radius of an oxygen atom.     

Relationship between sound insulation performance of walls and word intelligibility scores

Conversations must be shielded from people in an adjacent room if they include confidential information. Word intelligibility tests were performed in a total of 185 sound fields to examine the relationship between sound insulation performance and the degree of conversation leakage. The parameters of the test sound fields were background noise level in the adjacent room and the level difference between the two rooms. The background noise level was varied from 30 to 50 dB (A-weighted). The level difference was parametrically varied in terms of eight frequency characteristics and 10 absolute values. The results showed that word intelligibility scores were strongly correlated with the A-weighted speech-to-noise ratio and SNR_uni32. Equal-intelligibility contours, which can easily show the weighted level difference and A-weighted background noise level required to achieve a certain level of word intelligibility scores, were obtained from a multiple logistic regression analysis.     

Tetraaryl‐Substituted Benzo[1,2‐b:4,5‐b′]dipyrroles: Synthesis,Properties, and Applications to Hole‐Injection Materials in OLED Devices

Yes, HIMs can! A series of 2,3,6,7‐tetraarylbenzo[1,2‐b:4,5‐b′]dipyrroles (BDPs) were synthesized using zinc‐mediated double cyclization. Organic light‐emitting diodes consisting of BDP:PPB as a hole‐injection layer could be driven at a lower voltage than a PEDOT:PSS‐based device. Correlation of the IP values with the driving voltage shed some light on the mechanism of hole‐injection processes.

     

Simplified renormalization group method for ordinary differential equations

The renormalization group (RG) method for differential equations is one of the perturbation methods which allows one to obtain invariant manifolds of a given ordinary differential equation together with approximate solutions to it. This article investigates higher order RG equations which serve to refine an error estimate of approximate solutions obtained by the first order RG equations. It is shown that the higher order RG equation maintains the similar theorems to those provided by the first order RG equation, which are theorems on well-definedness of approximate vector fields, and on inheritance of invariant manifolds from those for the RG equation to those for the original equation, for example. Since the higher order RG equation is defined by using indefinite integrals and is not unique for the reason of the undetermined integral constants, the simplest form of RG equation is available by choosing suitable integral constants. It is shown that this simplified RG equation is sufficient to determine whether the trivial solution to time-dependent linear equations is hyperbolically stable or not, and thereby a synchronous solution of a coupled oscillators is shown to be stable.     

Carbon‐bridged Oligo(phenylenevinylene)s as Light‐harvesting Antenna for Porphyrins

The efficacy of carbon‐bridged oligo(phenylenevinylenes)s (COPVs) as light‐harvesting antenna for porphyrins is demonstrated using a series of 5,15‐di‐COPVn‐substituted free‐base and zinc porphyrins, COPVn‐MP‐COPVn (n=1–3, M=H₂, Zn). These molecules were synthesized by Suzuki–Miyaura cross‐coupling reactions of COPVn‐Bpin and Br‐H₂P‐Br . The absorption spectra of these compounds in solution show a significant expansion of the Soret band region together with a bathochromic shift of the Q band, suggesting a significant interaction between these chromophores in the ground state. The photoluminescence quantum yield of the porphyrin‐COPV conjugates is enhanced up to four times relative to the parent porphyrins. Theoretical calculations also indicated interactions between these chromophores in the HOMO, which suggests that the light‐harvesting ability stems from the expansion of the π‐electron‐conjugation system.