Publishing type：Research paper (scientific journal)   Publisher：Springer Science and Business Media LLC  

DOI： 10.1038/s41467-020-15988-1

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Other Link： http://www.nature.com/articles/s41467-020-15988-1

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

The front cover artwork is provided by the groups of Prof. Hiroshi Miyasaka (Osaka University, Japan), Prof. Masahiro Irie (Rikkyo University, Japan), Prof. Seiya Kobatake (Osaka City University, Japan) and Prof. Akira Sakamoto (Aoyama Gakuin University, Japan). The image shows the coherently vibrating closed form of a photochromic diarylethene derivative in the excited state, and subsequent structural evolution into the open form in the cycloreversion reaction. Read the full text of the Article at 10.1002/cphc.202000315.

DOI： 10.1002/cphc.202000550

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/cphc.202000551

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Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/anie.202006763

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Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/anie.202004583

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Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

DOI： 10.1021/jacs.0c02739

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Language：English   Publishing type：Research paper (scientific journal)  

A belt-shaped [8]cycloparaphenylene (CPP) and an enantioenriched Möbius-shaped [10]CPP have been synthesized by high-yielding rhodium-catalyzed intramolecular cyclotrimerizations of a cyclic dodecayne and a pentadecayne, respectively. This Möbius-shaped [10]CPP possesses stable chirality and isolated with high enantiomeric purity. It is evident from the reaction Gibbs energy calculation that the above irreversible cyclotrimerizations are highly exothermic; therefore establishing that the intramolecular alkyne cyclotrimerization is a powerful route to strained cyclic molecular strips.

DOI： 10.1021/jacs.9b06197

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

An important technique to realize novel electron- and/or proton-based functionalities is to use a proton-electron coupling mechanism. When either a proton or electron is excited, the other one is modulated, producing synergistic functions. However, although compounds with proton-coupled electron transfer have been synthesized, crystalline molecular compounds that exhibit proton-transfer-coupled spin-transition (PCST) behavior have not been reported. Here, we report the first example of a PCST Fe(II) complex, wherein the proton lies on the N of hydrazone and pyridine moieties in the ligand at high-spin and low-spin Fe(II), respectively. When the Fe(II) complex is irradiated with light, intramolecular proton transfer occurs from pyridine to hydrazone in conjunction with the photoinduced spin transition via the PCST mechanism. Because the light-induced excited high-spin state is trapped at low temperatures in the Fe(II) complex-a phenomenon known as the light-induced excited-spin-state trapping effect-the light-induced proton-transfer state, wherein the proton lies on the N of hydrazone, is also trapped as a metastable state. The proton transfer was accomplished within 50 ps at 190 K. The bistable nature of the proton position, where the position can be switched by light irradiation, is useful for modulating proton-based functionalities in molecular devices.

DOI： 10.1021/jacs.9b07204

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/cl.190141

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Publisher：Royal Society of Chemistry ({RSC})  

DOI： 10.1039/C9CC00455F

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

The compound [34](1,2,4,5)cyclophane, which consists of π-stacked two benzene rings, is one of the simplest dimeric molecules with a transannular π-π interaction. Its radical cation showed a characteristic near-infrared electronic absorption due to a transition from "bonding" to "anti-bonding" orbitals between the two benzene moieties. The Raman spectrum was measured in resonance with this electronic transition, and selective enhancement of low-frequency vibrational bands was observed. The strongest band at 241 cm-1 was assigned to one of the inter-ring vibrations that changed the distance between the two benzene rings. The Raman cross-section of this band was estimated to be 9.1 × 10-25 cm-2, which was comparable to typical resonance Raman cross-sections and 100 times stronger than those of the local ring-breathing vibrations (1230 and 1262 cm-1) of the radical cation. To understand this resonance Raman enhancement, the polarized Raman spectra were measured. The depolarization ratios of the cation bands were almost 1/3, which indicates an A-term rigorous resonance Raman effect with a contribution of a single electronic excited state. To analyze this A-term resonance Raman effect, the optimized geometry was calculated for the electronic excited S2 state of the radical cation responsible for its near-infrared electronic absorption. The bond lengths of the excited S2 state were almost the same as those of the ground state, while the distance between the two benzene rings extended by 7%. Large Franck-Condon factors were, thus, expected for the inter-ring vibrations, and resulted in the selective resonance Raman enhancement of these large amplitude vibrations.

DOI： 10.1039/c7cp06720h

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemical Society of Japan  

Water is still mysterious despite intensive and extensive studies over the years. Anomalous behavior of water as a liquid is yet to be fully comprehended. Here we show that the most generally known anomaly of water, the density maximum anomaly, is well accounted for by the formation of nanometersize ice crystallite at low temperatures. We show spectroscopically that, in cold and super-cooled water, this nanometer-size ice crystallite is formed and coexists with the other two forms of water. Multivariate hyperspectral analysis of 140 temperature dependent Raman spectra in the range of -23∼45 °C determines the three distinct vibrational spectra of the three forms of water and their fractions at different temperatures. Simulation based on the determined fractions successfully reproduces the temperature dependence of density with a maximum at the right temperature. The mystery of the density maximum of water has thus been given an unequivocal solution. The nanometer-size ice crystallite might well be called "nano-ice".

DOI： 10.1246/bcsj.20180052

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

A variety of fluorescent molecular viscosity probes have been widely used for mapping the local viscosity in cells and for monitoring the microenvironments in materials. However, their viscosity-sensing structural design still relies strongly on molecular rotors featuring intramolecular rotational dynamics. Here we report flapping molecules (FLAP) as a ratiometric viscosity-sensing fluorophore that shows polarity-independent dual fluorescence. Viscosity-sensing mechanism is based on a unique V-shaped-to-planar conformational change in the singlet excited state (S-1), in which the flexible motion of an eight-membered ring plays an important role. Fast conformational dynamics have been studied by time-resolved spectroscopies, and the viscochromic properties have been quantitatively analyzed. Application of FLAP to monitoring the curing process of epoxy resins has also been demonstrated, in which other typical environment-sensitive dyes did not work as a local viscosity probe.

DOI： 10.1039/c7tc01533j

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Delocalized biradicals have been extensively studied because of fundamental interests to singlet biradicals and several potential applications such as to two-photon absorption materials. However, many of the biradical studies only focus on the static properties of the rigid molecular structures. It is expected that the biradical properties of the delocalized biradicals are sensitive to the subtle changes of the molecular structures and their local environments. Therefore, the studies of the dynamic properties of the system will give further insight into stable radical chemistry. In this study, we directly probe the ultrafast dynamics of the delocalized biradical of a photochromic radical dimer, pentaarylbiimidazole (PABI), by time-resolved visible and infrared spectroscopies and quantum chemical calculations with the extended multistate complete active space second-order perturbation theory (XMS-CASPT2). While the photogenerated transient species was considered to be a single species of the biradical, the present ultrafast spectroscopic study revealed the existence of two transient isomers differing in the contributions of biradical character. The origin of the two metastable isomers is most probably due to the substantial van der Waals interaction between the phenyl rings substituted at the imidazole rings. Unraveling the temporal evolution of the biradical contribution will stimulate to explore novel delocalized biradicals and to develop biradical-based photofunctional materials utilizing the dynamic properties.

DOI： 10.1021/jacs.7b01598

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Delocalized biradicals have been extensively studied because of fundamental interests to singlet biradicals and several potential applications such as to two-photon absorption materials. However, many of the biradical studies only focus on the static properties of the rigid molecular structures. It is expected that the biradical properties of the delocalized biradicals are sensitive to the subtle changes of the molecular structures and their local environments. Therefore, the studies of the dynamic properties of the system will give further insight into stable radical chemistry. In this study, we directly probe the ultrafast dynamics of the delocalized biradical of a photochromic radical dimer, pentaarylbiimidazole (PABI), by time-resolved visible and infrared spectroscopies and quantum chemical calculations with the extended multistate complete active space second-order perturbation theory (XMS-CASPT2). While the photogenerated transient species was considered to be a single species of the biradical, the present ultrafast spectroscopic study revealed the existence of two transient isomers differing in the contributions of biradical character. The origin of the two metastable isome

DOI： 10.1021/jacs.7b01598

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Microscopic solvation environments in a prototype ionic liquid, bmimTf(2)N; 1-buty1-3-methyl-imidazoliumbis(trifluoromethanesulfonyl)imide, have been studied with the use of halides, X-2 and X-n(-) (X = I, Br; n = 3,5), as molecular probes. Resonance Raman spectroscopy has been used to detect these halogen species existing in bmimTf(2)N as well as in reference solvents including heptane, cyclohexane, KX/H2O and benzene. In heptane and cyclohexane, only free X-2 species are detected. In KX/H2O, only X-n(-) and, in benzene, only benzene-X-2 complexes are detected. On the contrary, free X-2 and X-n(-) are concomitantly detected in bmimTf(2)N, indicating that there are two distinct solvation environments in bmimTf(2)N, non-polar environments that solvate free X-2 and polar environments that stabilize X-n(-) These two distinct solvation environments are most likely to arise from microscopic structural heterogeneity of ionic liquids. (C) 2016 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.saa.2016.12.015

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The polarization switching mechanism is used in various devices such as pyroelectric sensors and memory devices. The change in polarization mostly occurs by ion displacement. The development of materials whose polarization switches via electron transfer in order to enhance operation speed is a challenge. We devised a synthetic and crystal engineering strategy that enables the selective synthesis of a [CrCo] heterometallic dinuclear complex with a polar crystal structure, wherein polarization changes stem from intramolecular charge transfer between co and the ligand. Polarization can be modulated both by visible-light irradiation and temperature change. The introduction of chiral ligands was paramount to the successful polarization switching in the valence tautomeric compound. Mixing Cr and Co complexes with enantiopure chiral ligands resulted in the selective formation of only pseudosymmetric [CrCo] heterometallic complexes. Furthermore, the left-handed chiral ligands preferentially interacted with their right-handed counterparts, enabling molecules to form a polar crystal structure.

DOI： 10.1021/jacs.6b05089

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：NATURE PUBLISHING GROUP  

We have developed an automatic and objective method for detecting human oral squamous cell carcinoma (OSCC) tissues with Raman microspectroscopy. We measure 196 independent Raman spectra from 196 different points of one oral tissue sample and globally analyze these spectra using a Multivariate Curve Resolution (MCR) analysis. Discrimination of OSCC tissues is automatically and objectively made by spectral matching comparison of the MCR decomposed Raman spectra and the standard Raman spectrum of keratin, a well-established molecular marker of OSCC. We use a total of 24 tissue samples, 10 OSCC and 10 normal tissues from the same 10 patients, 3 OSCC and 1 normal tissues from different patients. Following the newly developed protocol presented here, we have been able to detect OSCC tissues with 77 to 92% sensitivity (depending on how to define positivity) and 100% specificity. The present approach lends itself to a reliable clinical diagnosis of OSCC substantiated by the "molecular fingerprint" of keratin.

DOI： 10.1038/srep20097

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N-2. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti-Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation-vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N-2 pure rotational spectrum provides an accurate relative sensitivity curve (error similar to 5 x 10(-4)) in the wavenumber region of -150 to 150 cm(-1). We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright (C) 2015 John Wiley & Sons, Ltd.

DOI： 10.1002/jrs.4731

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER INST PHYSICS  

Raman spectroscopy of nano-scale materials is facing a challenge of developing a physically sound quantitative approach for the phonon confinement effect, which profoundly affects the phonon Raman band shapes of small particles. We have developed a new approach based on 3-dimensional phonon dispersion functions. It analyzes the Raman band shapes quantitatively in terms of the particle size distributions. To test the model, we have successfully obtained good fits of the observed phonon Raman spectra of diamond nanoparticles in the size range from 1 to 100 nm. (C) 2014 AIP Publishing LLC.

DOI： 10.1063/1.4864120

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Ultralow-frequency Raman spectroscopy that can measure vibrational bands at as low as +/- 10 cm(-1) has enabled facile in situ imaging of polycrystalline microstructures such as grains and grain boundaries with high polymorph specificity. We demonstrate this method by investigating microcrystals of two distinct polymorphs of 1,1'-binaphthyl using a microscope.

DOI： 10.1039/c4cc05955g

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER INST PHYSICS  

Low frequency vibrational spectra of submonolayer N3 dye (Ru(4,4'-dicarboxy-2,2'-bipyridine)(2)(NCS)(2)) adsorbed on TiO2 (110) were reported by using fourth-order coherent Raman spectroscopy, which is interface-sensitive vibrational spectroscopy. Most of the peaks observed in the experiment were at the same frequency as that of Raman and infrared spectra of the dye and TiO2. Two interfacial modes at 640 and 100 cm(-1) and one resonantly enhanced phonon at 146 cm(-1) appeared in addition to the pure TiO2 and N3 spectra. Adsorption of N3 dye on TiO2 contributed to the enhancement of 100 and 146 cm(-1) mode. The results not only reported interfacial low-frequency vibrations of TiO2 (110) with N3 dye adsorption but also suggested the coupling between the surface vibrations of TiO2 and charge transfer between N3 dye and TiO2 on the surface. (C) 2013 AIP Publishing LLC.

DOI： 10.1063/1.4807850

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER INST PHYSICS  

Rotational dynamics of solvated carbon dioxide (CO(2)) has been studied. The infrared absorption band of the antisymmetric stretch mode in acetonitrile is found to show a non-Lorentzian band shape, suggesting a non-exponential decay of the vibrational and/or rotational correlation functions. A combined method of a molecular dynamics (MD) simulation and a quantum chemical calculation well reproduces the observed band shape. The analysis suggests that the band broadening is almost purely rotational, while the contribution from the vibrational dephasing is negligibly small. The non-exponential rotational correlation decay can be explained by a simple rotor model simulation, which can treat large angle rotations of a relatively small molecule. A polarized Raman study of the symmetric stretch mode in acetonitrile gives a rotational bandwidth consistent with that obtained from the infrared analysis. A sub-picosecond time-resolved infrared absorption anisotropy measurement of the antisymmetric stretch mode in ethanol also gives a decay rate that is consistent with the observed rotational bandwidths. (C) 2012 American Institute of Physics. [doi:10.1063/1.3671998]

DOI： 10.1063/1.3671998

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

The melting process of 1-butyl-3-methylimidazolium chloride (bmimC1), a prototype room-temperature ionic liquid, has been studied with fast low frequency Raman spectroscopy. Simultaneous tracing of the lattice vibrations and trans/gauche conformational marker bands reveals that the conformational change in the butyl group occurs a few seconds after the loss of lattice vibrations. This finding indicates that the alkyl chain interaction in bmimC1 is so strong that the butyl conformation hardly changes in the very early stage of melting.

DOI： 10.1246/cl.2011.1308

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：AMER INST PHYSICS  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC APPLIED SPECTROSCOPY  

We have constructed a multi-channel Raman spectrometer that is capable of recording the low frequency region down to 5 cm(-1) with a measurement time of a few tenths of a second. An iodine vapor filter, which uses a narrow (similar to 0.03 cm(-1)cm(-1)) absorption line of iodine for Rayleigh scattering elimination, is combined with a multi-channel Raman spectrometer composed of a single polychromator and a charge-coupled device (CCD) camera. Thanks to the high Rayleigh scattering elimination efficiency of the filter, which is over 106, Raman spectra of microcrystalline L-cystine from -300 cm(-1) to 1000 cm(-1) are simultaneously measurable with a small gap of 10 cm(-1) (-5 cm(-1) to 5 cm(-1)). Although raw spectra contain many sharp spikes due to the fine structures of iodine absorption, they can be correctly compensated with the use of a transmittance spectrum measured under the same experimental conditions. Many Raman bands including the 9.8 cm(-1) band are measured with a high signal-to-noise ratio in both the Stokes and anti-Stokes sides with a measurement time as short as 0.2 s.

DOI： 10.1366/000370209788964368

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：English   Publisher：AMER CHEMICAL SOC  

We show several pieces of Raman spectroscopic evidence that are indicative of local structure formation in imidazolium-based ionic liquids. Low-frequency Raman spectra of C(n)mimX, where C(n)mim stands for 1-alkyl(CnH2n+1)-3-methylimidazolium cation and X represents the anion, exhibit broad bands assignable to collective modes of local structures. Spatial distributions of coherent anti-Stokes Raman scattering (CARS) signals from C(n)mim[PF(6)l are consistent with local structures whose size increases with increasing n. Picosecond Raman spectra of S, trans-stilbene as a "picosecond Raman thermometer" show microscopic thermal inhomogeneity ascribable to local structure formation in C(2)mimTf(2)N and C(4)mimTf(2)N. We also describe two novel phenomena that we believe are relevant to extraordinary nanoenvironments generated by local structures in a magnetic ionic liquid C(4)mim[FeCl4].

DOI： 10.1021/ar700074c

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Language：English   Publisher：AMER CHEMICAL SOC  

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