Coronenetetraimide‐Centered Cruciform Pentamers Containing Multiporphyrin Units: Synthesis and Sequential Photoinduced Energy‐ and Electron‐Transfer Dynamics

A series of coronenetetraimide (CorTIm)‐centered cruciform pentamers containing multiporphyrin units, in which four porphyrin units are covalently linked to a CorTIm core through benzyl linkages, were designed and synthesized to investigate their structural, spectroscopic, and electrochemical properties as well as photoinduced electron‐ and energy‐transfer dynamics. These systems afforded the first synthetic case of coroneneimide derivatives covalently linked with dye molecules. The steady‐state absorption and electrochemical results indicate that a CorTIm and four porphyrin units were successfully characterized by the corresponding reference monomers. In contrast, the steady‐state fluorescence measurements demonstrated that strong fluorescence quenching relative to the corresponding monomer units was observed in these pentamers. Nanosecond laser flash photolysis measurements revealed the occurrence of intermolecular electron transfer from triplet excited state of zinc porphyrins to CorTIm. Femtosecond laser‐induced transient absorption measurements for excitation of the CorTIm unit clearly demonstrate the sequential photoinduced energy and electron transfer between CorTIm and porphyrins, that is, occurrence of the initial energy transfer from CorTIm (energy donor) to porphyrins (energy acceptor) and subsequent electron transfer from porphyrins (electron donor) to CorTIm (electron acceptor) in these pentamers, whereas only the electron‐transfer process from porphyrins to CorTIm was observed when we mainly excite porphyrin units. Finally, construction of high‐order supramolecular patterning of these pentamers was performed by utilizing self‐assembly and physical dewetting during the evaporation of solvent.     

Synthesis of redox-active, intramolecular charge-transfer chromophores by the [2+2] cycloaddition of ethynylated 2H-cyclohepta[b]furan-2-ones with tetracyanoethylene

Ethynylated 2H-cyclohepta[b]furan-2-ones 5-15 have been prepared by Pd-catalyzed alkynylation of 3-iodo-5-isopropyl-2H-cyclohepta[b]furan-2-one (2) with the corresponding ethynylarenes or the reaction of 2-iodothiophene with 3-ethynyl-5-isopropyl-2H-cyclohepta[b]furan-2-one (4) under Sonogashira-Hagihara conditions. Compounds 5-15 reacted with tetracyanoethylene in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadducts, cyclobutenes, to afford the corresponding 1,1,4,4-tetracyanobutadienyl (TCBD) chromophores 16-26 in excellent yields. The intramolecular charge-transfer interactions between the 2H-cyclohepta[b]furan-2-one ring and TCBD acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel TCBD derivatives 16-26 was examined by cyclic voltammetry and differential pulse voltammetry, which revealed multistep electrochemical reduction properties, depending on the number of TCBD units in the molecule. Moreover, a significant color change was observed by UV/Vis spectroscopy under electrochemical reduction conditions.     

Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase

An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.     

Chiral Sc-catalyzed asymmetric Michael reactions of thiols with enones in water

Asymmetric Michael reactions of thiols with enones were catalyzed by a Sc(OTf)(3)-chiral bipyridine complex at room temperature in water without using any organic solvents, to afford the desired sulfides in high yields with high enantioselectivities.     

1,5]-H shift of aldehyde hydrogen in dienal compounds to produce ketenes

In 3-ethoxycarbonyl-2,4-dienal compounds, a thermal [1,5]-H shift of aldehyde hydrogen easily proceeded to produce the corresponding vinyl ketenes due to the remarkable substituent effect caused by the C3 ester group. The produced ketenes were captured by an alcohol and olefins to afford the corresponding esters and four-membered ring compounds, respectively.     

Compression behaviors of binary skutterudite CoP3 in noble gases up to 40 GPa at room temperature

The binary skutterudite CoP(3) has a large void at the body-centered site of each cubic unit cell and is, therefore, called a nonfilled skutterudite. We investigated its room-temperature compression behavior up to 40.4 GPa in helium and argon using a diamond-anvil cell. High-pressure in situ X-ray diffraction and Raman scattering measurements found no phase transition and a stable cubic structure up to the maximum pressure in both media. A fitting of the present pressure-volume data to the third-order Birch-Murnaghan equation of state yields a zero-pressure bulk modulus K(0) of 147(3) GPa [pressure derivative K(0)' of 4.4(2)] and 171(5) GPa [where K(0)' = 4.2(4)] in helium and argon, respectively. The Gru?neisen parameter was determined to be 1.4 from the Raman scattering measurements. Thus, CoP(3) is stiffer than other binary skutterudites and could therefore be used as a host cage to accommodate large atoms under high pressure without structural collapse.     

Phase transition in Pd40Ni10Cu30P20 bulk metallic glass under HP & HT

The phase transitions in Pd40Ni10Cu30P20 bulk metallic glass (BMG) have been studied under high pressure and high temperature (HP & HT) by X-ray diffraction measurements with synchrotron radiation source. We found that the BMG underwent a phase transitions of amorphous-crystalline-amorphous at 10 GPa upon heating. The parallel experiments were carried out at 7 GPa, while we did not observe the amorphous-crystalline-amorphous transitions by increasing temperature. Quenching the melted BMG at 7 GPa, it was found that the phase crystallized from the melt differed from the primary phase crystallized from the starting amorphous solid upon heating, suggesting there existed a distinct mechanism in two cases.     

Measurement of Fluorescence Quantum Yield of Ultraviolet-Absorbing Substance Extracted from Red Alga: Porphyra yezoensis and its Photothermal Spectroscopy

Optical properties of an ultraviolet-absorbing substance (UVAS) extracted from the marine red alga, Porphyra yezoensis, have been investigated. The substance is excited by UV light, and the emitted fluorescence is detected using an intelligent fluorescence detector. The fluorescence of UVAS is weaker by four orders of magnitude than the fluorescence intensity emitted by anthracene in the same optical system. The absorbed energy is apparently not transferred to the photosynthesis process and is believed to be consumed as heat. Using photothermal spectroscopy, a signal is observed indicating that the absorbed photon energy has transferred to the heat. The waveform of the photothermal signal of UVAS is similar to that of quinoxaline, whose fluorescence quantum yield is known to be zero. It is determined that the fluorescence quantum yield and the energy of the triplet state of UVAS are 1.7 ± 0.7 ± 10⁻⁴ and 21000 ± 1000 cm ⁻¹, respectively. The conclusion is that the excited molecules of UVAS decay by passing through the triplet state and dissipate all absorbed energy as heat.