Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy

The geometrical evolution of the reactant and formation of the photoproduct in the cycloreversion reaction of a diarylethene derivative were probed using time-resolved absorption spectroscopies in the visible to near-infrared and mid-infrared regions. The time-domain vibrational data in the visible region show that the initially formed Franck-Condon state is geometrically relaxed into the minimum in the excited state potential energy surface, concomitantly with the low-frequency coherent vibrations. Theoretical calculations indicate that the nuclear displacement in this coherent vibration is nearly parallel to that in the geometrical relaxation. Time-resolved mid-infrared spectroscopy directly detected the formation of the open-ring isomer with the same time constant as the decrease of the closed-ring isomer in the excited state minimum. This observation reveals that no detectable intermediate, in which the population is accumulated, is present between the excited closed-ring isomer and the open-ring isomer in the ground state.     

Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

Synthesis and deprotonation reactions of half‐sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of [{Cp*IrCl(μ‐Cl)}₂] (Cp*=η⁵‐C₅Me₅) with dimethylglyoxime (LH₂) at an Ir:LH₂ ratio of 1:1 afforded the cationic dioxime iridium complex [Cp*IrCl(LH₂)]Cl ( 1 ). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime–oximato complex [Cp*IrCl(LH)] ( 2 ) and the anionic dioximato(2?) complex K[Cp*IrCl(L)] ( 3 ) sequentially. Meanwhile, twofold deprotonation of the sulfato complex [Cp*Ir(SO₄)(LH₂)] ( 4 ) resulted in the formation of the oximato‐bridged dinuclear complex [{Cp*Ir(μ‐L)}₂] ( 5 ). X‐ray analyses disclosed their supramolecular structures with one‐dimensional infinite chain ( 1 and 2 ), hexagonal open channels ( 3 ), and a tetrameric rhomboid ( 4 ) featuring multiple intermolecular hydrogen bonds and electrostatic interactions.     

Macrocyclic Metal Complexes Bearing Rigid Polyaromatic Ligands: Synthesis and Catalytic Activity

We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes.     

Quantitative analysis of inhomogeneous luminance effect on visibility of text

In the present study, we measured the visibility of several types of Japanese text on a liquid crystal display (LCD) with a spatially inhomogeneous luminance and extended the visibility index function (VIF) to explain the current experimental results with a higher degree of accuracy. We quantitatively analyzed the effect of an inhomogeneous luminance, which was produced by the graphical representation of a background without reflected light and by reflected light on a homogeneous background. These results showed that the visibility of text was influenced by the inhomogeneity of the background luminance in a domain that depended on text size. Then we applied a weighted average background luminance with a two dimensional Gaussian function, whose distribution width was related to the text size, to VIF. Finally, we proposed a modified VIF and showed that the new method was able to precisely estimate the actual visibility of text with an inhomogeneous luminance.     

Optical simulation of reduced retinal illuminance caused by senile miosis

In order to simulate elderly vision for young observers, we developed an optical goggle using filters whose transmittance optically simulates the senile miosis: reduction in retinal illuminance as a function of ambient illuminance. First, we measured the pupil size of young and elderly subjects (mean age were 21.8 and 67.1 years, respectively) under six illuminance conditions (from 0.03 to 4850 lx), and formulated the relationship between illuminance and pupillary area functions in both age groups. Next, the transmittance formulae for the filter simulating the senile miosis were derived based on the properties of the pupillary area and visual functions of the elderly and the young subjects including the effect of mydriasis induced by the reduction of light due to the filter in young observers. Finally, we developed a goggle-type simulator using active optical devices which enables young people to experience senile miosis in any environment in real time.     

syn-selective direct catalytic asymmetric Mannich-type reactions of hydroxyketones using Y{N(SiMe3)2}3/linked-BINOL complexes

[reaction, structure: see text] Chiral Y{N(SiMe3)2}3/linked-BINOL catalyst generated Y-enolate in situ from various hydroxyketones (R2 = aryl, heteroaryl). Beta-amino-alpha-hydroxy ketones (R1 = aryl, heteroaryl, alkenyl) were obtained syn-selectively (up to 96/4) in high ee (up to 98%) and good yield (up to 98% yield).