記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry - An Asian Journal  

To detect small aromatic molecules in water, we prepared functional host molecules based on water-soluble N,N’-bis(2-aminobenzophenone)-1,4,5,8-naphthalenetetracarboxylic diimide (1) and a solubilizing agent using a high-speed vibration milling apparatus. The fluorescence response of host 1-solubilizing agent complexes before and after extraction of small aromatic guest molecules was large and the fluorescence maxima were dependent on the small aromatic guest molecules.

DOI： 10.1002/asia.202301015

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Angewandte Chemie - International Edition  

Self-inclusion complexes consisting of host-guest conjugates are one of the unique supramolecular structures because they form in-state and out-state depending on the external stimuli. Despite many reports of the stimuli-responsive self-inclusion complex formation, study of the structural relaxation from out-state to in-state by photoexcitation has been unexplored. Herein, we report that an electron-donating host and an electron-accepting guest conjugate exhibits the structural relaxation from out-state to in-state by photoexcitation. Formation of the in-state in the excited state resulted in exciplex emission along with the locally excited emission from the out-state. Moreover, this structural relaxation by photoexcitation was suppressed not only by temperature, but also by the presence of guest molecules, resulting in changes in the ratio of the dual emission intensities.

DOI： 10.1002/anie.202404409

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Inorganic Chemistry  

This study explored the development of functional dyes using aluminum, focusing on aluminum-based dinuclear triple-stranded helicates, and examined the effects of substituent variations on their structural and optical properties. Key findings revealed that the modification of methyl groups to the pyrrole positions significantly extended the conjugation system, resulting in a red shift in the absorption and emission spectra. Conversely, the modification of methyl groups at the methine positions due to steric hindrances increased the torsion angle of the ligands, leading to a blue shift in the absorption and emission spectra. A common feature across all complexes was that in the excited state, one of the three ligands underwent significant structural relaxation. This led to a pronounced Stokes shift and minimal spectra overlap with high photoluminescence behaviors. Moreover, our research extended to the optical resolution of the newly synthesized complexes by analyzing the chiroptical properties of the resulting enantiomers, including their circular dichroism and circularly polarized luminescence. These insights offer valuable contributions to the design and application of novel aluminum-based functional dyes, potentially influencing a range of fields, from materials science to optoelectronics.

DOI： 10.1021/acs.inorgchem.4c00045

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry Letters  

Three structural isomers of naphthalene diimides were synthesized. In all compounds, the electron-withdrawing diimide group exhibits a stable two-step reduction behavior under electrochemical conditions, and it was revealed that their reduction potentials vary significantly depending on the position of the diimide group relative to the naphthalene ring.

DOI： 10.1093/chemle/upad022

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry - An Asian Journal  

Abstract

Materials exhibiting room temperature phosphorescence (RTP) have recently emerged as a subject of significant interest. In this study, we successfully created inclusion crystals by introducing halobenzenes as guests into a host molecule combining benzophenone with naphthalene diimide. This approach led to the creation of fascinating fluorescence and RTP properties dependent on the guest molecules. Notably, crystals containing chlorobenzene showed cyan fluorescence, while those with iodobenzene displayed red RTP. This difference highlights the impact of the guest molecule on the luminescent properties, with the significant external heavy‐atom effect of iodobenzene playing a key role in promoting efficient intersystem crossing between the excited singlet and triplet states. Crystals with bromobenzene exhibited a unique blend of fluorescence and RTP, both from benzophenone and naphthalene diimide, highlighting the moderate heavy‐atom effect. These findings reveal composite materials with remarkably diverse and interesting optical characteristics.

DOI： 10.1002/asia.202301114

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記述言語：英語   出版者・発行元：Angewandte Chemie - International Edition  

This study reports an effective peripheral decoration of organic donor-acceptor diads with B(C6F5)3 for stabilizing electrogenerated radical ions. By employing a common p-type organic semiconductor benzothienobenzothiophene (BTBT) as the donor, tetracoordinate boron complexes showed improved solution electrochemiluminescence (ECL) intensity, reaching a 156-fold increase compared to that of the parent diad. The unprecedented Lewis-pairing-induced ECL enhancement is attributed to the multiple roles of B(C6F5)3: 1) redistributing frontier orbitals, 2) facilitating electrochemical excitation, and 3) restricting molecular motions. Furthermore, B(C6F5)3 converted the molecular arrangement of BTBT from conventional 2D herringbones into 1D π-stacks. This robust, highly ordered columnar nanostructure allowed red-shifting of the crystalline film ECL with electrochemical doping through the electronic coupling pathways of BTBT. Our approach will facilitate the development of elaborate metal-free ECL systems.

DOI： 10.1002/anie.202301109

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Materials Chemistry Frontiers  

Tetraarylated quinodimethanes, which are one of the overcrowded ethylenes, can adopt multiple conformations, such as folded, twisted, and other forms. However, it is difficult to obtain all of these conformations due to energy differences among them. To tackle this issue, we designed flexible polyaryl-substituted tetraazaanthraquinodimethanes (N4AQDs), in which a steric hindrance in the overcrowded fjord region was moderately reduced. As a result, X-ray analyses revealed that N4AQDs could adopt not only folded and twisted forms but also intermediate structures, e.g., planar and twisted-folded forms, in pseudopolymorphs. Since there is a large difference in the electronic configuration among conformers, the colour tone of crystals varied from yellow to red depending on the conformation of overcrowded N4AQDs. Notably, red to near-infrared emission was observed for the crystal containing twisted conformers. This is the first example of exceptionally flexible quinodimethanes with tunable photophysical properties and multi-chromic behaviour based on multiple conformations.

DOI： 10.1039/d2qm01199a

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/ange.202301109

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掲載種別：研究論文（学術雑誌）   出版者・発行元：New Journal of Chemistry  

Naphthalenediimide derivative-absorbed papers, which were prepared by dropping chloroform solution, showed fluorescence under photoirradiation after exposure to vapors of small aromatic guests. The fluorescence intensity and maximum wavelength depended on the type of guest aromatic molecules, similar to the crystal. The naphthalenediimide derivative-absorbed papers showed vapochromic and mechanochromic properties.

DOI： 10.1039/d2nj04929e

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of Materials Chemistry C  

The design and synthesis of novel circularly polarized luminescence (CPL) molecular emitters exhibiting photophysical modulation and high CPL efficiency have become an attractive research topic in synthetic and materials chemistry. In this study, three novel axially chiral tetra-BF2 complexes were rationally designed and synthesized with an easy synthetic approach. The novel terthiophene-substituted tetra-BF2 complexes were successfully prepared by the Suzuki-Miyaura coupling reaction with an isolated yield of 50% using Br-modified precursors. The terthiophene modification affected absorption, fluorescence, and CPL performance by extending the π-conjugation and improving intramolecular charge transfer (ICT) interactions. One compound, terthiophene modified in the meta-position relative to the pyridine moiety of a non-functionalized tetra-BF2 complex, exhibited a yellow-green emission, whereas another compound, terthiophene modified in the para-position, exhibited a yellow emission with a maximum bathochromic shift in both the absorption and emission bands. This is significantly different from unsubstituted and Br-modified compounds, which fluoresced in the green region by the π-π* transition. Moreover, the compound, in which the para-position to the pyridine part in the framework of the tetra-BF2 complex was substituted by terthiophene moieties, exhibited excellent CPL performance with a high dissymmetric factor (glum up to the order of 10−2) and CPL brightness (BCPL) at 125.2 M−1 cm−1 in toluene owing to the balance of electric and magnetic transition dipole moments compared with those of other tetra-BF2 complexes. This work opens a new avenue for developing novel organic CPL emitters by inducing ICT characters to modulate the emission color and high CPL efficiency.

DOI： 10.1039/d2tc04636a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：RSC Advances  

Benzophenone and its derivatives emit crystallization-induced phosphorescence despite their simple structures. To easily modify their phosphorescence properties, we prepared phosphorescence-emitting aqueous solutions of polysaccharide-benzophenone and polysaccharide-4,4′-difluorobenzophenone complexes, which exhibit excellent biocompatibility and biodegradability.

DOI： 10.1039/d2ra08205e

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記述言語：英語   出版者・発行元：Coordination Chemistry Reviews  

Pyrrole-containing metal complexes widely exist in nature, for example, vitamin B-12, heme, chlorophyll, and their derivatives. Each of them shows significant functions, which are essential for life. To mimic their important functions and substance conversion reactions, numerous pyrrole-containing metal complexes have been synthesized and investigated. This review mainly focuses on cobalt complexes having pyrrolecontaining ligands and the recent progress of molecular transformations catalyzed by the complexes, especially the vitamin B-12-related cobalt complexes and porphycene cobalt complexes. A variety of reaction systems, which enable a number of molecular transformations under mild conditions is described. The construction of new reaction systems and a combination of the materials inspired by natural systems is a promising and effective approach to realizing eco-friendly and cost-effective reaction systems. (C) 2022 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ccr.2022.214690

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出版者・発行元：Journal of Physical Chemistry C  

Rationally designed unsymmetric tri-BF2red to near-infrared (NIR) emitters were first reported in this study via a facile one-pot synthetic approach. The single-crystal structures and density functional theory calculations suggest their tunable conformation change around the bipyrrole part and unsymmetric structures in which three boron atoms are coordinated with the existing four different bidentate binding pockets, leaving two of the uncoordinated nitrogens in the pyrrole part. These novel tri-BF2emitters in the red to NIR region demonstrated ca. 30% of photoluminescence quantum yield (φPL) in toluene at room temperature and highly intense fluorescence at 77 K (up to 89% of φPLin 2-MeTHF), which is attributed to increased molecular flexibility and enhanced intramolecular charge transfer interactions resulting from symmetry breaking. The photophysical modulation in multi-BF2complexes was achieved by the coordinated number of BF2units, providing a step forward to understanding and guiding the design of the most efficient versatile emissive organoboron compounds.

DOI： 10.1021/acs.jpcc.2c05511

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry - An Asian Journal  

N,N’-Dipyrid-3-yl-1,4,5,8-naphthalenediimide linked to two tris(pentafluorophenyl)borane (1) exhibits strong fluorescence emission in the solid state by the formation of a charge-transfer complex containing small aromatic guest molecules. Hydrophobic 1 was dissolved in water by mixing with poly-L-lysine (PLL) as a solubilizing agent. The 1-PLL complex could include small aromatic guest molecules in water, significantly increasing the fluorescence. The fluorescence maxima of 1 in aqueous solution and solid state were different depending on the guest molecule. Therefore, compound 1 was prepared as aqueous solution with information of fluorescence on solids by complexation with PLL.

DOI： 10.1002/asia.202200879

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その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/asia.202200879

出版者・発行元：Journal of Porphyrins and Phthalocyanines  

One-pot synthetic approach to produce trifluoroacetamide has been developed using an electrochemical method with the B12 complex as a catalyst under mild conditions, in open air at room temperature. Thirty examples of trifluoroacetamide were synthesized from 1,1,1-trichloro-2,2,2-trifluoroethane (CFC-113a) in moderate to good yields. This user-friendly strategy is compatible with a broad range of trifluoroacetamide syntheses.

DOI： 10.1142/S1088424621500292

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Angewandte Chemie - International Edition  

This study reports the facile syntheses of tetra-boron difluoride (tetra-BF2 ) complexes, flag-hinge-like molecules that exhibit intense green-to-orange luminescence in solution and yellow-to-red emission in the solid states. Single-crystal structure analysis and density functional theory calculations suggested a bent structure of this series of compounds. The complexes also exhibited excellent optical properties, with quantum yields reaching 100 % and a large Stokes shift. These properties were attributed to the altered bending angle of the molecule in the S1 excited state. As the rotational motion was suppressed around the 2,2'-bipyrrole axis, atropisomers with axial chirality were formed, which are optically resolvable into (R) and (S)-enantiomers through a chiral column. The atropisomers thus function as circularly polarized luminescent (CPL) materials, in which the color (green, green-yellow, and yellow) can be varied by controlling the aggregation state. This rational design of multi-BF2 complexes can potentially realize novel photofunctional materials.

DOI： 10.1002/anie.202204358

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of Porphyrins and Phthalocyanines  

A new meso-tetrakis(3,5-di-tert-butylphenyl) substituted porphycene and its cobalt complex were synthesized and characterized. Several meso-tetraarylporphycene cobalt complexes having different substituents showed catalytic activity for the hydrogen gas evolution reaction (HER) in the presence of trifluoroacetic acid (TFA) under electrochemical reductive conditions. The electrochemical potential of the HER was -1.50V vs. Ag/AgCl in THF. The active species of this reaction were determined to be the ligand reduced species of Co(II) porphycenes. The catalytic efficiencies of the cobalt complexes of meso-aryl substituted porphycenes and meso-tetraphenylporphyrin were compared and meso-tetraphenyl porphycene cobalt complex exhibited the best current efficiency of 72%. Based on these experimental results and theoretical calculations, we proposed a possible HER mechanism of this system.A new porphycene having four 3,5-di-tert-butylphenyl groups at the meso-positions and its cobalt complex were synthesized and characterized. The electrocatalytic hydrogen evolution reaction via the ligand-centered reduction of porphycene cobalt complexes was investigated. The reaction process was revealed by experimental results and theoretical calculations and was clearly different from the system via metal-centered reduction using porphyrin cobalt complex.

DOI： 10.1142/S108842462250016X

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出版者・発行元：Chemistry Letters  

The aggregation state of two new covalently bonded dinuclear boron-based dye complexes was controlled to fabricate white-light-emitting materials. The materials exhibit blue and orange emission, with a photoluminescence quantum yield of 16% for one of the complexes in the solid state. This study highlights the importance of molecular engineering through the control of dye aggregation as a fundamental technology for creating novel functional materials with interesting optical properties.

DOI： 10.1246/cl.210794

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

X-ray diffraction, neutron diffraction, and theoretical calculations were used to investigate the relationship between the optical properties and degree of protonation in acid-base complexes. We prepared five acid-base complexes by using a pyridine-modified pyrrolopyrrole derivative and salicylic acid. Two of the prepared acid-base complexes were polymorphs of guest-free crystals with green emission; the other three were guest-inclusion crystals with yellow emission containing CH2 Cl2 , CH2 Br2 , or C2 H4 Cl2 . The presence or absence of guests caused the emission to change color, altering the hydrogen bond strength between the acid-base complexes. Accurate N⋅⋅⋅H distances between the pyridyl moiety and the carboxy group over the temperature range 123 to 273 K were 1.40 Å for the guest-free crystals and 1.25 Å for the guest-inclusion crystals. Our findings contribute to a better understanding of the complex relationship between photofunction and proton dynamics in acid-base complexes.

DOI： 10.1002/chem.202103044

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8DMSO (2·8DMSO), where H2mna = 2-mercaptonicotininc acid, DMF = N,N'-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms 1 and 2, have been characterized by FTIR, UV-Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters 1·7DMF and 2·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (λex = 365 nm), the solvated hexasilver(I) cluster 2·8DMSO gives intense greenish-yellow photoluminescence in the solid state (λPL = 545 nm, ΦPL = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster 1·7DMF displays PL in the near-IR region (λPL = 765 nm, ΦPL = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (ΦPL < 0.01) is observed. The desorption-sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH⋯π interactions, and π⋯π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement.

DOI： 10.3390/molecules26216731

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Electrochemical transformations of DDT into oxygen-incorporated products, amides and esters, catalyzed by a B-12 derivative, heptamethyl cobyrinate perchlorate, have been developed under aerobic conditions. The dechlorinative oxygenation of DDT forms the acyl chloride as an intermediate for the synthesis of the amide and ester in the reaction with the amine and alcohol, respectively. This electrochemical method demonstrated with 20 oxygen-incorporated dechlorinated products up to 88% yields with 15 new compounds and was also successfully applied to the conversion of methoxychlor to an amide and ester.

DOI： 10.1246/bcsj.20210316

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Directly investigating hydrogen bond (HB) dynamics in molecular materials is a challenging task. Here, we report a set of porphyrin isomers, porphycenes, that visualize slight changes on the order of picometers in the intramolecular HB dynamics. Intramolecular HBs of porphycenes were regulated by the systematic modification at meso positions with methyl (Me), cyclopentyl (Cy5), and cyclohexyl (Cy6) moieties. Notably, the quantum yields varied from 35 to 0.04% in chloroform, depending on a slight distortion in the porphycene framework. SC-XRD, XPS, and NMR clearly revealed that the Me and Cy6 moieties increased the nonradiative deactivation by strengthening the intramolecular NH···N HBs whereas Cy5 retained their photoluminescence properties. This is the first example of how the distortion of planar porphyrinoids at the picometer level along with the strength of the intramolecular NH···N HBs can drastically affect their optical properties. The results revealed new avenues of HB engineering based on porphyrinoids.

DOI： 10.1021/acs.jpclett.1c03020

記述言語：英語   掲載種別：研究論文（学術雑誌）  

For post-transition metal electrocatalytic hydrogen evolution reaction (HER), the new porphycene antimony complexes, Sb(III)OEPo and Sb(V)OEPo-Br-2, were synthesized and characterized. Based on the electrochemical and electro-spectro measurements, the two-step one-electron reduction processes of Sb(III)OEPo were indicated to be both ligand-centered and the irreversible reduction process observed for Sb(V)OEPo-Br-2 was assigned to be the reduction from Sb(V)OEPo-Br-2 to Sb(III)OEPo. Electrocatalytic HER proceeded at -1.0 V (vs. Ag/AgCl) under acidic conditions via the ligand-centered reductions. The electron accepting nature of the porphycene ligand enabled the utilization of a main-group element as a central element for the ligand-centered HER at anodically shifted potentials.

DOI： 10.1246/bcsj.20210177

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Invited for the cover of this issue is Toshikazu Ono, Yoshio Hisaeda and co-workers at Kyushu University and their collaborators at Ochanomizu University, Chuo University, and Institute for Molecular Science. The image depicts a molecular assembly structure shining like a jewel, glowing in the red-to-near infrared region. Read the full text of the article at 10.1002/chem.202100906.

DOI： 10.1002/chem.202101685

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Room-temperature phosphorescence (RTP) emitters have attracted significant attention. However, purely organic RTP emitters in red to near-infrared region have not been properly investigated. In this study, a series of naphthalenediimide- halobenzoate -linked molecules are synthesized, one of which exhibits efficient RTP properties, showing red to near-infrared emission in solid and aqueous dispersion. Spectroscopic studies and single-crystal X-ray diffraction analysis have shown that the difference in the stacking modes of compounds affects the optical properties, and the formation of intermolecular charge-transfer complexes of naphthalenediimide-halobenzoate moiety results in a bathochromic shift of absorption and RTP properties. The time-dependent density functional theory calculations showed that the formation of charge-transfer triplet states and the external heavy atom effect of the halogen atom enhance the intersystem crossing between excited singlet and triplet states.

DOI： 10.1002/chem.202100906

記述言語：英語   掲載種別：研究論文（学術雑誌）  

New chiroptical chromophores, dinuclear triple-stranded helicates, composed of tetradentate ligands with aluminum(III) ions, are described. These are synthesized in two steps using inexpensive pyrrole derivatives, hydrazine, and aluminum chloride. These molecular architectures (ALPHY) show multi-color (cyan, yellow, and orange) photoluminescence in solution and in the solid-state, which depends on the substituents of the ligands. The photoluminescence quantum yields of helicates were up to 54 &#37;. The right-handed (P) and left-handed (M) helicates are so stable that they do not undergo racemization in some solvents and are mirror images according to circular dichroism and circularly polarized luminescence (CPL) with an absolute luminescence dissymmetry factor (g ) of up to the 10 order. Mixing the different helicates produces white-light emission with CPL characters. This study offers a glimpse into the potential applications of chromophores with diverse photophysical properties. lum −3

DOI： 10.1002/anie.202011450

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20200295

記述言語：その他   掲載種別：研究論文（学術雑誌）  

The first boron complexes of porphycenes, structural isomers of porphyrin, are reported. They are synthesized in good yields by reacting the free-base porphycene ligands with BF ·Et O through a microwave-assisted method. Depending on the substituent group of porphycenes, two different coordination structures, mono- and diboron porphycenes, are obtained simultaneously. The single crystal structures and DFT calculations suggest that the boron atom of the monoboron porphycene is favorably coordinated on the dipyrroethene site, and the regioisomer of diboron porphycene is of cisoid stereochemistry, which is more stable than transoid. We also investigate the protonation behavior of boron porphycene complexes. Diboron porphycene does not undergo protonation, whereas monoboron porphycene undergoes protonation at the nonboron coordinating pyrroline site, resulting in a red shift in both absorption and emission spectra. Protonation and deprotonation of monoboron porphycene can be reversibly triggered using acids and bases. 3 2

DOI： 10.1021/acs.inorgchem.0c01266

記述言語：英語   掲載種別：研究論文（学術雑誌）  

記述言語：その他   掲載種別：研究論文（学術雑誌）  

A rational design to create vapoluminescence materials is to install fluorescent tags into molecules. Changing the distance and arrangement of the fluorescent tags can be performed to trigger the vapoluminescence behavior. Herein, we unexpectedly observed a vapoluminescence behavior triggered by a crystal-state host-guest complexation between pillar[6]arene host crystals and organic guest vapors that both exhibit no fluorescence in the visible-light region. After the uptake of the guest vapors, the host-guest complex crystals exhibit blue fluorescence in the visible-light region. Charge-transfer interactions between the host and guest molecules in the crystal state mainly contribute to the observation of fluorescence in the visible-light region.

DOI： 10.1021/acs.cgd.0c00982

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two new photoluminescent multinuclear Cu(I) cluster complexes supported by monoanionic bidentate ligandN-methylbenzimidazolethiolate (Me-bimt(-)), [Cu-n(Me-bimt)(n)] withn = 4 (1) and 6 (2), have been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. For1and2, the Cu(I) ions and the Me-bimt(-)ligands construct a cubane-type {Cu4S4} and a hexagonal-prism {Cu6S6} frameworks, respectively. In the crystalline state, complexes1and2exhibit green (lambda(em) = 500 nm) and near-infrared (lambda(em) = 876 nm) emission, respectively, under UV irradiation (lambda(ex) = 365 nm) at room temperature. Both crystals reveal temperature-dependent dual emission below 200 K: complex1emits in the visible wavelength region (lambda(em) = 493 and 542 nm) and complex2in the visible to near-infrared wavelength region (lambda(em) = 752 and 973 nm) which are attributed to multiple photoexcited states at the cluster frameworks with distinct metal nuclearity.

DOI： 10.1007/s11696-020-01251-w

記述言語：その他   掲載種別：研究論文（学術雑誌）  

A proof-of-concept for the one-step, synthetically challenging cyclic and acyclic perfluoroalkylation of (hetero)arenes driven by the valence change of a vitamin B12 derivative as a cobalt catalyst in the presence of fluoroalkylating reagents (X(CF2)4X) is presented. The consecutive formation of cobalt-carbon bonds and generation of fluoroalkyl radicals by homolysis are the key steps for the reaction to proceed.

DOI： 10.1039/d0ra05295g

記述言語：英語   掲載種別：研究論文（学術雑誌）  

In this study, the ring contracting skeletal rearrangement reaction in one-pot under basic conditions from octaethylporphycene to two types of isocorroles, i.e., the meso-formyl and meso-free forms, was confirmed and the reaction mechanism was proposed by the comparative analyses of the experimental and theoretical studies. The electron accepting nature of the porphycene and imine-amine conversion of pyrrole rings make it possible to react with hydroxide ions and the following reaction to afford isocorroles. Based on this reaction, the valence of the compound as a ligand as well as the photochemical and electrochemical properties were dramatically changed.

DOI： 10.1002/ejoc.201901659

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/ejoc.202000226

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The cobalt complexes of meso-aryl substituted porphycenes were synthesized and characterized. The reduction potentials of the complexes were shifted to the positive side depending on the strength of the electron-withdrawing properties of the meso-substituents, while the optical properties, such as the absorption spectra of these complexes, were similar. This suggests that the energy levels of the molecular orbitals of the complexes were changed by the meso-substituents while the gaps of the orbitals were not significantly changed. The one-electron reduction of the complex did not afford the Co(I) species, but the ligand-reduced radical anion, which was characterized by electrospectrochemistry. The generated ligand-reduced species reacted with alkyl halides to form the Co(III)-alkyl complex. As a result, the reduction potential of the electrolytic reaction could be directly controlled by the substituents of the porphycene. The catalytic reaction with trichloromethylbenzene was also performed and it was found that the ratio of the obtained products was changed by the reduction potentials of the catalyst, i.e. the cobalt porphycenes.

DOI： 10.1142/S1088424619500780

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Mechanistic Study on Ring Contracting Skeletal Rearrangement from Porphycene to Isocorrole by the Combination of Experimental and Theoretical Studies

記述言語：英語   掲載種別：研究論文（学術雑誌）  

meso-Tetraalkyl porphycenes exhibit unique optical properties with wide potential applications. The very fact that incorporation of porphycenes into polymeric materials is rare, make this approach a particularly attractive one. In this work, meso-tetrakis(3-butenyl)porphycene bearing four terminal olefin groups is prepared via two synthetic strategies: 1) the McMurry reaction using 5,5′-diacyl-2,2′-bipyrroles as precursors and 2) the oxidative coupling of dipyrroethenes. The newly obtained porphycene has been characterized by single X-ray crystallography. A porphycene–polydimethylsiloxane hybrid film is successfully prepared by a platinum-catalyzed hydrosilylation reaction. The hybrid film can be anchored with tweezers, showing a weak red emission with a quantum yield of 0.4 % at room temperature, whose intensity drastically increases reaching a quantum yield of 6.7 % in liquid nitrogen (77 K). This report represents the first example of porphycene-containing elastomeric films for potential application in various fields.

DOI： 10.1002/ejoc.201901497

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The series of donor-acceptor (D-A) compounds consisting of a thianthrene donor and either a benzophenone or a diphenylsulfone acceptor units were designed and synthesized via Suzuki cross-coupling. By varying the number of donor units, as well as by introducing heavy atom (Br) into the molecular structure the impact of these substituents on the thermal, electrochemical and emissive properties of the compounds was studied. The compound containing two thianthrene units appeared to have higher thermal stability and higher glass transition temperature than monosubstituted derivative. All thianthrenyl substituted benzophenone or diphenylsulfone compounds showed bipolar behavior. Strong room temperature phosphorescence and dual fluorescence-phosphorescence were observed at room temperature. The compounds containing stronger electron acceptor diphenylsulfone demonstrated a two-fold higher photoluminescence quantum yield values up to 19% in rigid Zeonex^® films than that benzophenone derivatives. The crystals of some synthesized compounds demonstrated oxygen sensing ability.

DOI： 10.1016/j.dyepig.2019.107605

記述言語：その他  

Bipolar thianthrene derivatives exhibiting room temperature phosphorescence for oxygen sensing

DOI： 10.1016/j.dyepig.2019.107605

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The main obstacle to the widespread application of porphycenes lies in the lack of efficient and economical methods for their production. Discovery of new synthetic methodologies for porphycene derivatives are important for fine-tuning of their optical and electrochemical properties. Herein, the preparation of a set of AABB-, ABAB-, and ABBA-type meso-tetrasubstituted unsymmetric porphycenes is reported. Their synthesis involved the acid-catalyzed oxidative coupling of AA- and BB-dipyrroethenes, or AB-type dipyrroethenes, as precursors in yields of up to 19 %. The structures were unambiguously confirmed by X-ray crystallography. The type and position of substituents in the unsymmetric porphycenes enabled fine-tuning of the optical and electronic properties, which are discussed in terms of their UV/Vis absorption, fluorescence spectroscopies, cyclic voltammetry, and density functional theory calculations.

DOI： 10.1002/chem.201902080

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Vapochromism, chromism induced by vapor desorption/absorption, has received considerable attention in recent years due to its potential applications in chemical sensors for toxic gases and vapors. In this paper, a set of naphthalene diimide (NDI) derivatives with various bulky groups is investigated for chromogenic and fluorogenic detection of small aromatic molecules in the vapor phase. Among the studied compounds, NDI with a 2-benzophenone unit in its structure exhibited a unique vapochromic/vapoluminescent behavior toward toluene, p-xylene, 4-fluorotoluene, and anisole. Detection limits in the parts-per-million (ppm) range are accomplished with some compounds. Optical measurements and X-ray crystal structure analyses clearly suggested that intermolecular charge-transfer interactions between the electron-deficient NDI and the electron-rich aromatic guest molecules as well as the inherent porosity of the sensor materials contribute to their unique sensing abilities. Discrimination of xylene isomers was demonstrated by taking advantage of selective inclusion phenomena. Two binary sensor ensembles, including our previously reported NDI derivative, enable the construction of a mini-sensor array that can be used to discriminate benzene derivatives-including xylene isomers-with the naked eye. The present simple, low-cost, metal-free, and effective sensor materials may promote practical applications with advantages relative to other known sensor materials.

DOI： 10.1039/c9tc03140e

記述言語：その他  

Salt-cocrystal continuum for photofunction modulation: stimuli-responsive fluorescence color-tuning of pyridine-modified intramolecular charge-transfer dyes and acid complexes

DOI： 10.1039/c9tc02524c

記述言語：その他  

Symmetry Reduction of Porphycenes with Finely Tuned Optical and Electronic Properties through Oxidative Cyclization of E/Z-Mixed Dipyrroethenes

DOI： 10.1002/chem.201902080

記述言語：その他  

Highly malleable haem-binding site of the haemoprotein HasA permits stable accommodation of bulky tetraphenylporphycenes

DOI： 10.1039/c9ra02872b

記述言語：英語  

Electrochemical properties and catalytic reactivity of cobalt complexes with redox-active meso-substituted porphycene ligands

記述言語：その他  

Front Cover: Visible Light‐Driven, One‐pot Amide Synthesis Catalyzed by the B 12 Model Complex under Aerobic Conditions (ChemPlusChem 3/2019)

DOI： 10.1002/cplu.201800587

記述言語：その他  

Visible Light-Driven, One-pot Amide Synthesis Catalyzed by the B-12 Model Complex under Aerobic Conditions

DOI： 10.1002/cplu.201800522

記述言語：その他  

Flexible-color tuning and white-light emission in three-, four-, and five-component host/guest co-crystals by charge-transfer emissions as well as effective energy transfers

DOI： 10.1039/c8tc06165c

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Invited for this month's cover is the group of Prof. Dr. Hisashi Shimakoshi at Kyushu University, Japan. The front cover shows “le mariage” of an iridium complex and a vitamin B
₁₂
derivative with two wedding rings in the background. This collaboration of two complexes is induced by visible light in the presence of air to achieve green molecular transformations. This protocol was applied to the synthesis of amides from a wide range of trichlorinated organic compounds. Read the full text of the article at 10.1002/cplu.201800522.

DOI： 10.1002/cplu.201800586

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A visible light responsive catalytic system with the B ₁₂ complex as the catalyst and [Ir(dtbbpy)(ppy) ₂ ]PF ₆ as the photosensitizer was developed. It provides a convenient and efficient way to synthesize amides. Based on this method, trichlorinated organic compounds were converted into amides in the presence of an amine under aerobic conditions at room temperature in a one-pot procedure. Various trichlorinated organic compounds and an amine source, such as primary, secondary, and cyclic amines, have been evaluated for this transformation, providing the expected products in moderate to excellent yields. Notably, product formation depended on the reaction atmosphere where the amide was obtained under aerobic conditions while partially dechlorinated products were obtained under anaerobic conditions. As this protocol is free from hazardous reagents, extra additives, noble metals, and dangerous gas, the present method provides a novel and efficient approach for amide synthesis under mild and easily controlled conditions.

DOI： 10.1002/cplu.201800522

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Three-, four-, and five-component host/guest crystals with multi-color and white light emission is described. Our strategy is based on the confinement of aromatic donor guests in supramolecular acceptor hosts. The supramolecular acceptor hosts (NDI-TPFB) were composed of N,N′-dipyrid-3-yl-1,4,5,8-naphthalenediimide (NDI) with two tris(pentafluorophenyl)borane (TPFB) linked by boron-nitrogen dative bonds as Lewis acid-base pairs, which spontaneously formed upon mixing the components. In the first part, a set of three-component crystals with 14 different aromatic guests were characterized to elucidate the structure-property relationships. In the latter part, a series of 17 types of four- and five-component crystals were formed with the use of binary or ternary guest inclusion systems, and their structural and photophysical properties were investigated. Among them, 14 types of crystals were formed effectively without destroying the crystal structure, as determined by X-ray diffraction and fluorescence microscopy. Notably, flexible color tuning, including white light emission, was realized by tuning the guest ratio and the combinations. Various intermolecular interactions such as C-H⋯F interactions, π-π stacking, charge-transfer interactions, and inclusion phenomena were important for forming the crystals. This approach that yields a rational solution of multicomponent crystals could be potentially useful for obtaining novel photofunctional solid-state systems.

DOI： 10.1039/c8tc06165c

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The synthesis of difluoromethylated (CF ₂ R) (R=H, alkyl/aryl, CO ₂ R, etc.) compounds has received considerable attention in recent years. In this study, the cobalt(III)−carbon-mediated catalytic C−H difluoroacylation of unactivated arenes and heteroarenes using BrCF ₂ CO ₂ Et is reported. This catalytic cycle is based on a valence change of the cobalt catalyst, a naturally derived vitamin B ₁₂ derivative, driven by controlled-potential electrolysis at −0.8 V vs. Ag/AgCl under visible-light irradiation in dimethyl sulfoxide. A broad substrate scope is demonstrated, and two compounds were characterized according to their X-ray crystal structures. Mechanistic studies showed that the reaction proceeds through a radical pathway mediated by homolytic cleavage of the cobalt(III)–carbon bond. A turnover number of more than 100 was observed, owing to the inherent stability of the vitamin B ₁₂ framework. This naturally derived catalytic system has potential applications in medicinal chemistry and materials science.

DOI： 10.1002/celc.201900164

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Vapochromism, chromism induced by vapor desorption/absorption, has received considerable attention in recent years due to its potential applications in chemical sensors for toxic gases and vapors. In this paper, a set of naphthalene diimide (NDI) derivatives with various bulky groups is investigated for chromogenic and fluorogenic detection of small aromatic molecules in the vapor phase. Among the studied compounds, NDI with a 2-benzophenone unit in its structure exhibited a unique vapochromic/vapoluminescent behavior toward toluene, p-xylene, 4-fluorotoluene, and anisole. Detection limits in the parts-per-million (ppm) range are accomplished with some compounds. Optical measurements and X-ray crystal structure analyses clearly suggested that intermolecular charge-transfer interactions between the electron-deficient NDI and the electron-rich aromatic guest molecules as well as the inherent porosity of the sensor materials contribute to their unique sensing abilities. Discrimination of xylene isomers was demonstrated by taking advantage of selective inclusion phenomena. Two binary sensor ensembles, including our previously reported NDI derivative, enable the construction of a mini-sensor array that can be used to discriminate benzene derivatives - including xylene isomers - with the naked eye. The present simple, low-cost, metal-free, and effective sensor materials may promote practical applications with advantages relative to other known sensor materials.

DOI： 10.1039/c9tc03140e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Iron(iii)- and cobalt(iii)-9,10,19,20-tetraphenylporphycenes, which possess bulky phenyl groups at the four meso positions of porphycene, were successfully incorporated into the haem acquisition protein HasA secreted by Pseudomonas aeruginosa. Crystal structure analysis revealed that loops surrounding the haem-binding site are highly flexible, remodelling themselves to accommodate bulky metal complexes with significantly different structures from the native haem cofactor.

DOI： 10.1039/c9ra02872b

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The regulation of proton transfer dynamics between acid-base complexes is of significant interest in the pharmaceutical industry and materials chemistry. However, the extent of proton transfer in the solid state is difficult to predict, and identifying the salts (protonation), cocrystals (hydrogen bond), and salt-cocrystal continuum (partially protonated states) remain challenging topics. Here we report that the three states (salts/cocrystals/salt-cocrystal continuum) can be distinguished by photoluminescent color changes based on acid-base complexes consisting of a pyridine-modified pyrrolopyrrole dye and organic acids. Structure-property relationships of 10 complexes indicated that ΔpK_a value (pK_a (protonated base)-pK_a (acid)) and the crystalline environment determine the extent of proton transfer, which governs the intramolecular charge-transfer (ICT) strength of the complexes and tunes the photoluminescence properties. Enhancement of the ICT strength leads to a bathochromic shift of emission from blue to green to yellow under UV light. The salt-cocrystal continuum (0 < ΔpK_a < 3) showed vapochromism/vapofluorochromism against CH₂Cl₂, owing to the extent of proton transfer from the acid to the pyridine moiety of the dye being modulated by inclusion and desorption of CH₂Cl₂. This study suggests that the rational design of photoluminescent acid-base complexes is useful for obtaining novel photofunctional materials.

DOI： 10.1039/c9tc02524c

記述言語：その他  

Switching of Monomer Fluorescence, Charge-Transfer Fluorescence, and Room-Temperature Phosphorescence Induced by Aromatic Guest Inclusion in a Supramolecular Host

DOI： 10.1002/chem.201804349

記述言語：その他  

Learning from B-12 enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis

DOI： 10.3762/bjoc.14.232

記述言語：その他  

Synthesis of Trifluoromethylated B-12 Derivative and Photolysis of Cobalt(III)-Trifluoromethyl Bond

DOI： 10.1246/cl.180355

記述言語：その他  

Piezofluorochromism in Charge-Transfer Inclusion Crystals: The Influence of High Pressure versus Mechanical Grinding

DOI： 10.1002/cptc.201700227

リポジトリ公開URL： https://hdl.handle.net/2324/7237117

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Polymer-based room-temperature-phosphorescent (RTP) materials are attractive alternatives to low-molecular-weight organic RTP compounds because they can form self-standing transparent films with high thermal stability. However, their RTP lifetimes in air are usually short (&lt
≈0.4 s). Here, the simple organic amorphous polymer, poly(styrene sulfonic acid) (PSS), exhibits an ultralong RTP lifetime in air when desiccated. The maximum lifetime is 1.22 s, which is three times that of previously reported RTP amorphous organic polymers. The lifetime can be controlled by the PSS molecular weight and by the ratio of sulfonic acid groups introduced into the polymer. The dry polymers should enable unprecedented molecular engineering in organic molecule-based optoelectronic devices because of the self-standing and thermal stability attributes.

DOI： 10.1002/adfm.201707369

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two novel meso- dicycloalkylporphycenes, namely meso- dicyclopentyl-(Cy5Pc) and meso-dicyclohexylporphycenes (Cy6Pc) are synthesized for the first time in porphycene chemistry. We use intermolecular oxidative coupling of 5,6-dicycloalkydipyrroethenes mediated by hypervalent iodine(III) reagents. The solution fluorescence maxima of Cy5Pc are more than 400 times as intense as that of Cy6Pc. The results suggested that photoluminescence switching is achieved through the ring strain perturbation of the meso-substituted cycloalkyl groups on the porphycene cavity.

DOI： 10.1039/c7cc07170a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The electrochemical trifluoromethylation and perfluoroalkylation of aromatic compounds mediated by a vitamin B-12 derivative as a cobalt-based catalyst has been developed. The Co(I) species of a vitamin B-12 derivative, prepared by controlled-potential electrolysis at -0.8 V vs. Ag/AgCl in methanol, reacted with RfI (R-f = CF3, n-C3F7, n-C4F9, n-C8F17, and n-C10F21) to form a Co-R-f complex. This complex released an R-f radical under visible light irradiation, which then reacted directly with non-activated (hetero) arenes to form the desired fluoroalkylated molecules through direct C-H functionalization. To our knowledge, this is the first report of a naturally derived vitamin B-12 catalyzed trifluoromethylation and perfluoroalkylation of aromatic compounds as a cobalt-mediated catalyst.

DOI： 10.1039/c7cc06221d

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The preparation of the polymers having a self-attractive urea unit via hydrogen bonding and a selfrepulsive lipophilic ion unit via electrostatic interaction was carried out to achieve the thermoresponsivity of polymer solution. The solubility of the obtained copolymers depended on the balance between the attractive force induced by hydrogen bonding among the urea units and the repulsive force attributed to the dissociation of the ionic units. In aprotic and nonpolar solvents, the solubility of the polymers was changed from insoluble to soluble with the increasing content of the ionic units. Moreover, in acetonitrile and 1,2-dichloroethane, the UCST-type thermoresponsivity was observed. This result indicated that the UCST-type thermoresponsivity was induced by cleavage of the hydrogen bonds among urea units upon heating, and at the cloud point, the repulsive force among the ionic units overwhelmed the attractive force. From the result of this research, we would like to emphasize that the combination of a lipophilic ion pair and other self-attractive units can be a simple principle for the molecular design of UCST-type thermoresponsive polymers in any media.

DOI： 10.1039/c7py00591a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Inclusion crystals were effectively formed from a simple naphthalenediimide derivative with toluene, 4-fluorotoluene, and p-xylene by the aid of cooperative intermolecular interactions, such as charge-transfer interactions and inclusion phenomena. The crystals showed intense guest-dependent solid-state emission based on ground state CT complexes between naphthalenediimide and small aromatic guests.

DOI： 10.1246/cl.170122

記述言語：英語   掲載種別：研究論文（学術雑誌）  

meso-Tetraalkylporphycenes were synthesized in a few steps using intramolecular oxidative coupling of the Z-isomer of 5,6dialkyldipyrroethenes. The use of a hypervalent iodine(III) reagent, namely phenyliodine(III) bis(trifluoroacetate), is essential for performing these reactions.

DOI： 10.1246/cl.161019

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Benzene, toluene, ethylbenzene, the isomers of xylene, and trimethylbenzene are harmful volatile organic compounds and pose risks to human health and the environment. However, there are currently no effective chemosensors for vapors of these compounds. A porous supramolecular host for turn-on fluorogenic and chromogenic detection of the vapors of small aromatic hydrocarbons is presented. The host was constructed from a naphthalenediimide derivative that was supramolecularly connected to tris(pentafluorophenyl)borane. The amorphous powder form of the host allowed for effective accommodation of vapors of small aromatic hydrocarbons, resulting in a guest-dependent fluorescence emission. Increases in the fluorescence yield of 76-, 46-, and 37-fold were observed with toluene, benzene, and m-xylene, respectively. Negligible responses were obtained with common organic solvents. This simple supramolecular host could be applied as a useful sensor of small aromatic hydrocarbon vapors.

DOI： 10.1002/chem.201601812

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A supramolecular conjugate of myoglobin (Mb) and water-soluble poly(acrylate), (PA(5k) and PA(25k), where 5k and 25k represent the molecular weight of the polymers, respectively), is constructed on the basis of a noncovalent heme-heme pocket interaction. The modified heme with an amino group linked to the terminus of one of the heme-propionates is coupled to the side-chain carboxyl groups of poly(acrylate) activated by N-hydroxysuccinimide. The ratios of the heme-modified monomer unit and the unmodified monomer unit (m:n) in the polymer chains of Heme-PA(5k) and Heme-PA(25k) were determined to be 4.5:95.5 and 3.1:96.9, respectively. Subsequent addition of apoMb to the conjugated polymers provides Mb-connected fibrous nanostructures confirmed by atomic force microscopy. A mixture of the heme-modified polymer and dimeric apomyoglobin as a cross-linker forms a microgel in which the reconstituted myoglobin retains its native exogenous ligand binding activity.

DOI： 10.1002/asia.201501415

記述言語：英語   掲載種別：研究論文（学術雑誌）  

In this study, polystyrene (PS) ionomers having tetraalkylammonium with a series of counterions are prepared with various feed ratio of the ionic units and blended with nonionic poly(n-butyl methacrylate) (PBMA) which is originally immiscible with PS. According to differential scanning calorimetry analysis, in the blends of ionomers with tetraarylborate and PBMA, the ionomers with more than 1 mol% of the ionic units are completely miscible with PBMA. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction measurements reveal that the bulky and lipophilic ion-pair inhibits the association of ions and instead induces the attractive interaction to alkyl groups of PBMA. Tensile tests of the miscible specimen exhibit both characteristic behavior, that is, high tensile strength as PS and high elongation property of PBMA.

DOI： 10.1002/macp.201500281

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.inorgchem.5b02129

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Simple yet ubiquitous multimolecular assembly systems with color-tunable emissions are realized by cooperative electron donor acceptor interactions, such as the boron nitrogen (B-N) dative bond as a Lewis acid base pair and charge transfer (CT) interactions. These are ternary-component systems consisting of a naphthalenediimide derivative (NDI), tris-(pentafluorophenyl)borane (TPFB), and aromatic molecules (guest) with an NDI:TPFB:guest ratio of 1:2:2. The crystal shows guest-dependent color-tunable emissions such as deep blue to orange when a guest molecule of benzene is replaced with other pi-conjugated systems. A good correlation between the emission wavelength and ionization potential of the guest and electronic structure calculations indicated that the emission is due to the CT transition from the guest to the NDI. The present study suggests that a rational solution of multcomponent molecular puzzles would be useful for obtaining novel photofunctional solid-state systems.

DOI： 10.1021/jacs.5b04178

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The repair of oxidative damage to DNA is essential to avoid mutations that lead to cancer. Oxidized DNA bases, such as 8-oxoguanine, are a main source of these mutations, and the enzyme 8-oxoguanine glycosylase 1 (OGG1) is the chief human enzyme that excises 8-oxoguanine from DNA. The activity of OGG1 has been linked to human inflammation responses and to cancer, and researchers are beginning to search for inhibitors of the enzyme. However, measuring the activity of the enzyme typically requires laborious gel-based measurements of radiolabeled DNAs. Here we report the design and properties of fluorogenic probes that directly report on the activity of OGG1 (and its bacterial homologue Fpg) in real time as the oxidized base is excised. The probes are short, modified DNA oligomers containing fluorescent DNA bases and are designed to utilize 8-oxoguanine itself as a fluorescence quencher. Screening of combinations of fluorophores and 8-oxoguanine revealed two fluorophores, pyrene and tCo, that are strongly quenched by the damaged base. We tested 42 potential probes containing these fluorophores: the optimum probe, OGR1, yields a 60-fold light-up signal in vitro with OGG1 and Fpg. It can report on oxidative repair activity in mammalian cell lysate and with bacterial cells overexpressing a repair enzyme. Such probes might prove useful in quantifying enzyme activity and performing competitive inhibition assays.

DOI： 10.1002/cbic.201500184

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Crystal structures and solid-state emission properties of tetraalkyl 4,4'-dimethyl-2,2'-bipyrrole-3,3',5, 5'-tetracarboxylates (alkyl = methyl, ethyl, and isopropyl) have been investigated. Single crystal X-ray diffraction studies revealed that all bipyrroles are co-planar due to an intramolecular hydrogen bonding. The isopropyl derivative exhibited a C=O center dot center dot center dot pi interaction in the solid-state and showed the longest emission wavelength because of increase in structural flexibility. (C) 2015 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2015.01.159

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A non-precious metal catalyst (NPMC) promoting a four-electron oxygen reduction reaction (ORR) was synthesized by heat treatment of myoglobin (Mb) containing a heme (iron protoporphyrin IX) as a source of iron, nitrogen, and carbon atoms. Samples of the mixture of Mb and carbon black (Vulcan XC72R: VC) were pyrolyzed at 740, 840, 940, 1040 or 1140 degrees C under N-2 flow. The microstructures of the carbonized Mb catalysts were characterized by XRD, Raman spectroscopy, XPS, and TEM. Results indicate that the iron-containing active site is embedded within the surface structure in an amorphous domain of the carbon materials. The catalyst ink in a 0.05 wt% Nafion solution in isopropanol was coated onto a glassy carbon electrode and the ORR activity of Mb-based NPMCs was evaluated in a rotating disk electrode experiment in an O-2-saturated 0.1 M HClO4 solution at 25 degrees C. The catalyst synthesized at 940 degrees C has the highest ORR activity in terms of the onset potential and the current density. In contrast, pyrolytic temperatures above 940 degrees C decrease the activity, suggesting that the active structure of the catalyst apparently decomposes at higher temperatures. The Koutecky-Levich plots indicate that the Mb-based catalyst prepared at 940 degrees C catalyzes four-electron ORR (n = ca. 4). The catalysts prepared at other temperatures have n values of 3.6 at 740 degrees C, 3.7 at 840 degrees C, and 2.9 at 1040 degrees C. The ORR of Mb/VC is diffusion-controlled at potentials lower than 0.3 V (vs. RHE) and the onset potential is 0.84 +/- 0.01 V.

DOI： 10.1142/S108842461550039X

記述言語：英語   掲載種別：研究論文（学術雑誌）  

We report the development of simple fluorogenic probes that report on the activity of both bacterial and mammalian uracil-DNA glycosylase (UDG) enzymes. The probes are built from short, modified single-stranded oligonucleotides containing natural and unnatural bases. The combination of multiple fluorescent pyrene and/or quinacridone nucleobases yields fluorescence at 480 and 540 nm (excitation 340 nm), with large Stokes shifts of 140-200 nm, considerably greater than previous probes. They are strongly quenched by uracil bases incorporated into the sequence, and they yield light-up signals of up to 40-fold, or ratiometric signals with ratio changes of 82-fold, on enzymatic removal of these quenching uracils. We find that the probes are efficient reporters of bacterial UDG, human UNG2, and human SMUG1 enzymes in vitro, yielding complete signals in minutes. Further experiments establish that a probe can be used to image UDG activity by laser confocal microscopy in bacterial cells and in a human cell line, and that signals from a probe signalling UDG activity in human cells can be quantified by flow cytometry. Such probes may prove generally useful both in basic studies of these enzymes and in biomedical applications as well.

DOI： 10.1093/nar/gkt309

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Polyelectrolytes are ubiquitous materials, and their unique properties originate from dissociation of ionic groups to the small number of macromolecular ions and the large number of small counterions. They have been exploited only in water or high-dielectric media and scarcely in nonpolar ones (epsilon < 10). Herein, we demonstrate that poly(octadecyl acrylate) bearing tetraalkylammonium tetraarylborate as ionic groups behaves as a polyelectrolyte in the common nonpolar organic solvents such as chloroform, THF, and 1,2-dichloroethane. Conductivity measurement, DOSY NMR spectroscopy, and viscosity measurements clearly indicate that they form the extended conformation in them. This result emphasizes that the ionic polymers bearing suitable ion pairs ionizable in the given media act as polyelectrolytes. Various characteristic properties and processes of polyelectrolytes should be realized in nonpolar media by designing ion pairs and polymer chains in the ionic polymers. Moreover, our results imply that electrostatic interaction is readily available as a long-range repulsive force even in the nonpolar media.

DOI： 10.1021/mz3002879

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two kinds of oppositely charged polystyrene ionomers bearing the bulky and lipophilic phosphazenium cation or diborateimidazolide anion that are soluble and dissociated partially into ions even in nonpolar solvents were prepared. Alternate complexes of them were fabricated in less-polar solvent, acetone, layer-by-layer onto a gold substrate and silica nanoparticles.

DOI： 10.1246/cl.2011.648

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Molecular design of lipophilic polyelectrolyte gels as superabsorbent polymers that exhibit a high degree of swelling in less-polar and nonpolar organic solvents is demonstrated. A small amount of tetraalkylammonium tetraphenylborate with long alkyl chains as a lipopholic ion pair is incorporated into crosslinked polyacrylates with variable alkyl chain lengths to provide novel lipophilic polyelectrolyte gels. Their swelling degree becomes more than 100 times as much as their dried weights in various organic solvents. The high effectiveness of the swellable solvents shifts to the polar ones by decreasing the length of the alkyl chain. Swelling or collapsing of the lipophilic polyelectrolyte gels originates from both incompatibility of the polymer chains in the media and dissociation of ionic groups. Thus, a unique superabsorbency is observed when the polymer chains have good compatibility with the solvents and the solvents have relatively high polarities enough to dissociate the ionic groups. By varying the polarity of the neutral monomer in these polyelectrolyte gels, the design of gels that can absorb solvents of nearly any polarity is demonstrated.

DOI： 10.1002/adfm.200801221

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Polyelectrolyte gels that are known as super- absorbent polymers swell and absorb water up to several hundred times their dried weights and have become ubiquitous and indispensable materials in many applications(1,2). Their superior swelling abilities originate from the electrostatic repulsion between the charges on the polymer chains and the osmotic imbalance between the interior and exterior of the gels(3). However, no superabsorbent polymers for volatile organic compounds ( VOCs), and especially for nonpolar organic solvents (epsilon < 10) have been reported, because common polyelectrolyte gels collapse in such solvents(4-6) owing to the formation of a higher number of aggregates of ions and ion pairs(7,8). Here, we report that a novel class of polyelectrolyte gels bearing tetra- alkylammonium tetraphenylborate(9,10) as a lipophilic and bulky ionic group swell in some nonpolar organic solvents up to 500 times their dry size. Dissociation of the ionic groups even in low- dielectricmedia ( 3 < epsilon < 10) enhances the swelling ability by expansion of the polymer networks(3). This expands the potential of polyelectrolytes that have been used only in aqueous solutions or highly polar solvents(11), and provides soft materials that swell in a variety of media. These materials could. nd applications as protective barriers for VOCs spilled in the environment and as absorbents for waste oil.

DOI： 10.1038/nmat1904

開催年月日： 2015年11月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：広島大学霞キャンパス   国名：日本国  

開催年月日： 2015年9月

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開催地：奈良女子大学   国名：日本国  

開催年月日： 2015年9月

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開催地：奈良女子大学   国名：日本国  

開催年月日： 2015年9月

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開催年月日： 2015年7月

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開催地：メルパルク京都   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2015年3月

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開催地：九州大学 伊都キャンパス   国名：日本国  

開催年月日： 2014年12月

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開催地：広島大学 東広島キャンパス   国名：日本国  

開催年月日： 2014年11月

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開催年月日： 2014年10月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北海道札幌市・北海道大学   国名：日本国  

開催年月日： 2014年10月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北海道札幌市・北海道大学   国名：日本国  

開催年月日： 2014年6月

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開催年月日： 2014年3月

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開催地：名古屋大学 東山キャンパス   国名：日本国  

開催年月日： 2014年3月

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開催地：名古屋大学 東山キャンパス   国名：日本国  

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開催地：日本大学理工学部船橋キャンパス   国名：日本国  

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記述言語：日本語  

開催地：日本大学理工学部船橋キャンパス   国名：日本国  

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国名：日本国  

開催年月日： 2015年11月

記述言語：日本語  

開催地：広島大学霞キャンパス   国名：日本国  

開催年月日： 2015年9月

記述言語：日本語  

開催地：奈良女子大学   国名：日本国  

開催年月日： 2015年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：奈良女子大学   国名：日本国  

開催年月日： 2015年9月

記述言語：日本語  

開催地：奈良女子大学   国名：日本国  

開催年月日： 2015年9月

記述言語：日本語  

開催地：奈良女子大学   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2015年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：千葉県船橋市・日本大学理工学部船橋キャンパス   国名：日本国  

開催年月日： 2014年10月

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開催年月日： 2014年10月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北海道札幌市・北海道大学   国名：日本国  

開催年月日： 2014年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：東京都文京区・中央大学   国名：日本国  

開催年月日： 2014年9月

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開催年月日： 2014年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：東京都文京区・中央大学   国名：日本国  

開催年月日： 2014年9月

記述言語：日本語   会議種別：口頭発表（一般）  

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開催年月日： 2014年7月

記述言語：英語  

開催地：北海道札幌市・ロイトン札幌   国名：日本国  

開催年月日： 2014年7月

記述言語：英語   会議種別：口頭発表（一般）  

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開催年月日： 2014年6月

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開催地：福岡県北九州市・北九州国際会議場   国名：日本国  

開催年月日： 2014年6月

記述言語：日本語  

開催地：福岡県北九州市・北九州国際会議場   国名：日本国  

開催年月日： 2014年6月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：福岡県北九州市・北九州国際会議場   国名：日本国  

開催年月日： 2014年6月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：福岡県北九州市・北九州国際会議場   国名：日本国  

開催年月日： 2014年6月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北海道札幌市・北海道大学   国名：日本国  

開催年月日： 2014年3月

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開催年月日： 2014年3月

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開催地：名古屋大学 東山キャンパス   国名：日本国  

開催年月日： 2014年3月

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開催地：名古屋大学 東山キャンパス   国名：日本国  

開催年月日： 2014年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：名古屋大学 東山キャンパス   国名：日本国  

開催年月日： 2014年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：名古屋大学 東山キャンパス   国名：日本国  

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開催年月日： 2013年11月

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開催地：韓国ソウル Hoam Faculty House   国名：日本国  

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開催年月日： 2013年11月

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開催年月日： 2013年11月

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開催地：琉球大学千原キャンパス   国名：日本国  

開催年月日： 2013年11月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：琉球大学千原キャンパス   国名：日本国  

開催年月日： 2013年11月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：琉球大学千原キャンパス   国名：日本国  

開催年月日： 2013年11月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：琉球大学千原キャンパス   国名：日本国  

開催年月日： 2013年11月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：琉球大学千原キャンパス   国名：日本国  

開催年月日： 2013年11月

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開催地：琉球大学千原キャンパス   国名：日本国  

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開催地：名古屋大学 東山キャンパス   国名：日本国  

開催年月日： 2013年9月

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開催地：愛媛大学 城北キャンパス   国名：日本国  

開催年月日： 2013年9月

記述言語：日本語   会議種別：口頭発表（一般）  

国名：日本国  

開催年月日： 2013年8月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：唐津ロイヤルホテル   国名：日本国  

開催年月日： 2013年7月

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開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年7月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北九州国際会議場・北九州市小倉北区   国名：日本国  

開催年月日： 2013年5月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：京都国際会館   国名：日本国  

開催年月日： 2013年3月

記述言語：日本語  

開催地：立命館大学BKC、滋賀   国名：日本国  

開催年月日： 2013年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：立命館大学KBC、滋賀   国名：日本国  

開催年月日： 2013年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：立命館大学BKC、滋賀   国名：日本国  

開催年月日： 2013年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：立命館大学BKC、滋賀   国名：日本国  

開催年月日： 2013年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：立命館大学BKC、滋賀   国名：日本国  

記述言語：日本語  

開催地：岡山大学創立50周年記念館   国名：日本国  

記述言語：その他  

Vapochromic materials, which change color and luminescence when exposed to specific vapors and gases, have attracted considerable attention in recent years owing to their potential applications in a wide range of fields such as chemical sensors and environmental monitors. Although the mechanism of vapochromism is still unclear, several studies have elucidated it from the viewpoint of crystal engineering. In this mini-review, we investigate recent advances in the vapochromism of organic crystals. Among them, macrocyclic molecules and inclusion complexes, which have apparent host–guest interactions with analyte molecules (specific vapors and gases), are described. When the host compound is properly designed, its cavity size and symmetry change in response to guest molecules, influencing the optical properties by changing the molecular inclusion and recognition abilities. This information highlights the importance of structure–property relationships resulting from the molecular recognition at the solid–vapor interface.

DOI： 10.3390/sym12111903

記述言語：英語  

© 2019 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim meso-Tetraalkyl porphycenes exhibit unique optical properties with wide potential applications. The very fact that incorporation of porphycenes into polymeric materials is rare, make this approach a particularly attractive one. In this work, meso-tetrakis(3-butenyl)porphycene bearing four terminal olefin groups is prepared via two synthetic strategies: 1) the McMurry reaction using 5,5′-diacyl-2,2′-bipyrroles as precursors and 2) the oxidative coupling of dipyrroethenes. The newly obtained porphycene has been characterized by single X-ray crystallography. A porphycene–polydimethylsiloxane hybrid film is successfully prepared by a platinum-catalyzed hydrosilylation reaction. The hybrid film can be anchored with tweezers, showing a weak red emission with a quantum yield of 0.4 &#37; at room temperature, whose intensity drastically increases reaching a quantum yield of 6.7 &#37; in liquid nitrogen (77 K). This report represents the first example of porphycene-containing elastomeric films for potential application in various fields.

DOI： 10.1002/ejoc.201901497

記述言語：その他  

© 2019 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim Invited for this month&#039;s cover is the group of Prof. Dr. Hisashi Shimakoshi at Kyushu University, Japan. The front cover shows “le mariage” of an iridium complex and a vitamin B 12 derivative with two wedding rings in the background. This collaboration of two complexes is induced by visible light in the presence of air to achieve green molecular transformations. This protocol was applied to the synthesis of amides from a wide range of trichlorinated organic compounds. Read the full text of the article at 10.1002/cplu.201800522.

DOI： 10.1002/cplu.201800586

記述言語：その他  

© 2019 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim Invited for this month&#039;s cover picture is the group of Yoshio Hisaeda at Kyushu University (Japan). The cover picture shows the electrochemical activation of a vitamin B12 derivative and the obtained difluoroacylated products. Read the full text of the Article at 10.1002/celc.201900164.

DOI： 10.1002/celc.201901155

記述言語：その他  

© 2019 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim The synthesis of difluoromethylated (CF 2 R) (R=H, alkyl/aryl, CO 2 R, etc.) compounds has received considerable attention in recent years. In this study, the cobalt(III)−carbon-mediated catalytic C−H difluoroacylation of unactivated arenes and heteroarenes using BrCF 2 CO 2 Et is reported. This catalytic cycle is based on a valence change of the cobalt catalyst, a naturally derived vitamin B 12 derivative, driven by controlled-potential electrolysis at −0.8 V vs. Ag/AgCl under visible-light irradiation in dimethyl sulfoxide. A broad substrate scope is demonstrated, and two compounds were characterized according to their X-ray crystal structures. Mechanistic studies showed that the reaction proceeds through a radical pathway mediated by homolytic cleavage of the cobalt(III)–carbon bond. A turnover number of more than 100 was observed, owing to the inherent stability of the vitamin B 12 framework. This naturally derived catalytic system has potential applications in medicinal chemistry and materials science.

DOI： 10.1002/celc.201900164

記述言語：英語   掲載種別：記事・総説・解説・論説等（学術雑誌）  

Cobalamins (B₁₂) play various important roles in vivo. Most B₁₂-dependent enzymes are divided into three main subfamilies: adenosylcobalamin-dependent isomerases, methylcobalamin-dependent methyltransferases, and dehalogenases. Mimicking these B₁₂ enzyme functions under non-enzymatic conditions offers good understanding of their elaborate reaction mechanisms. Furthermore, bio-inspiration offers a new approach to catalytic design for green and eco-friendly molecular transformations. As part of a study based on vitamin B₁₂ derivatives including heptamethyl cobyrinate perchlorate, we describe biomimetic and bioinspired catalytic reactions with B₁₂ enzyme functions. The reactions are classified according to the corresponding three B₁₂ enzyme subfamilies, with a focus on our recent development on electrochemical and photochemical catalytic systems. Other important reactions are also described, with a focus on radical-involved reactions in terms of organic synthesis.

DOI： 10.3762/bjoc.14.232

記述言語：日本語  

新規なポルフィセンリン錯体の合成とその酸化還元挙動

記述言語：日本語  

新規なアンチモンポルフィセン錯体の合成と性質

記述言語：日本語  

記述言語：日本語  

記述言語：日本語  

新規なポルフィセン15族元素錯体の合成とその電気化学的特性について

記述言語：日本語  

ポルフィセンリン錯体の合成と光・電気化学物性

記述言語：日本語  

新規なリンポルフィセン錯体の合成と構造および酸化還元挙動

記述言語：日本語  

記述言語：日本語  

新規なポルフィセン15族元素錯体の合成とその物性

記述言語：日本語  

自己組織化を利用した多核金属錯体のメゾスコピック超分子構造体形成とその特性

記述言語：日本語  

ポルフィリン構造異性体を集積化した電解重合薄膜の創製及びそのエレクトロクロミック特性

記述言語：日本語  

多核錯体を集積化した環状構造体への修飾基導入法の開拓

記述言語：日本語  

自己組織化を利用した多核金属錯体のメゾスコピック超分子構造体形成とその特性

記述言語：日本語  

ポルフィリン構造異性体を集積化した電解重合薄膜の作製とそのエレクトロクロミック特性

記述言語：日本語  

多核クラスターユニットの事前修飾による機能性高分子錯体の合成

記述言語：日本語  

ポルフィリン構造異性体を集積化した電解重合薄膜の作製とそのエレクトロクロミック特性

記述言語：日本語  

自己組織化を利用した多核金属錯体のメゾスコピック超分子構造体形成とその特性

記述言語：日本語  

ビタミンB₁₂誘導体のコバルト‐ヒドリド錯体を用いた有機合成反応の開拓

記述言語：日本語  

ビタミンB₁₂誘導体を触媒とした電解トリフルオロメチル化触媒反応

記述言語：日本語  

ポルフィリン構造異性体を集積化した電解重合薄膜の作製とそのエレクトロクロミック特性

記述言語：日本語  

多孔性有機結晶のナノ空間を利用した芳香族炭化水素の高感度蛍光検出

記述言語：日本語  

多孔性有機結晶のナノ空間を利用した強発光性室温リン光材料の創製

記述言語：日本語  

多核クラスターユニットの事前修飾による機能性高分子錯体の合成

記述言語：日本語  

新規イミダゾール修飾ポルフィセンの合成

記述言語：日本語  

新規オキシム型二核コバルト錯体の合成とその性質

記述言語：日本語  

ビタミンB₁₂誘導体を触媒とするトリフルオロメチル化反応

記述言語：日本語  

多核錯体を集積化したメタロ超分子ポリマーの創製とレドックス特性

記述言語：日本語  

コバルトポルフィセン錯体の配位子還元体を活性種とした反応とその機構

記述言語：日本語  

ポルフィリン環を含むRu十二核箱型クラスターの合成,構造および溶液内挙動

記述言語：日本語  

ルテニウムポルフィセン重合薄膜の合成及びそのエレクトロクロミック特性

記述言語：日本語  

ビタミンB₁₂誘導体を触媒とするラジカル的トリフルオロメチル化反応の開発

記述言語：日本語  

非金属ポルフィセンの化学:新規リンポルフィセンの合成と発光挙動

記述言語：日本語  

Ru三核錯体とポルフィリンを含む多核箱形クラスターの合成とホストゲスト相互作用

記述言語：日本語  

トリフルオロメチル基を軸配位子とするビタミンB₁₂誘導体の合成と性質

記述言語：日本語  

ビタミンB₁₂誘導体を用いた有機ハロゲン化合物からの電気化学的物質変換反応

記述言語：日本語  

ビタミンB₁₂‐Ru光増感剤系への電子メディエーターの導入とその応用

記述言語：日本語  

多座配位子を末端に有する多核金属錯体の合成と物性

記述言語：日本語  

発光性包接結晶の分子設計:多色,白色,室温リン光材料へのアプローチ

記述言語：日本語  

発光性包接結晶の分子設計:固相合成法の適用

記述言語：日本語  

重合部位を有する新規ポルフィセン金属錯体の合成

記述言語：日本語  

コバルトポルフィセン錯体類の酸化還元挙動と酸化的付加反応

記述言語：日本語  

非金属ポルフィセンの化学:新規リンポルフィセンの合成

記述言語：日本語  

コバルトポルフィセンの配位子レドックスを利用した触媒的脱ハロゲン化反応

記述言語：日本語  

コバルト錯体とバイオマスを用いた光駆動型水素発生触媒系の構築

記述言語：日本語  

ホウ素‐窒素錯形成を利用した超分子複合体の固相合成法の構築と固体発光特性の評価

記述言語：日本語  

ポルフィリンとルテニウム三核錯体をユニットとする多核箱型クラスターの構築とホストゲスト相互作用

記述言語：日本語  

水素化ポルフィセン金属錯体の合成と酸化還元特性

記述言語：日本語  

軸位連結型ルテニウム(II)ポルフィリン‐ランタノイド(III)二核錯体の合成と発光特性

記述言語：日本語  

長鎖アルキル修飾ルテニウム三核錯体の合成とその自己集合特性

記述言語：日本語  

可視光駆動型ビタミンB₁₂高分子触媒の開発と物質変換反応への応用

記述言語：日本語  

コバルトポルフィセンの配位子レドックスを利用した酸化的付加反応

記述言語：日本語  

非金属ポルフィセン化学の開拓:新規リンポルフィセンの合成

記述言語：日本語  

コバルトポルフィセンの配位子還元を利用したCo‐C結合の形成反応

記述言語：日本語  

ポルフィリン環を含む多核箱形クラスターの合成と溶液内ホストゲスト相互作用

記述言語：日本語  

メタロセン集積型金属クラスターの合成と電子特性

記述言語：その他  

We previously report development of a new class of ionic polymer gels having lipophilic ion-pairs that consist of a lipophilic tetraphenylborate anion and a quaternary ammonium cation with long alkyl chains. They swelled largely in the less polar solvents as &#039;super-absorbent&#039; ionic polymer gels. The driving force of the large swelling was osmotic pressure induced by dissociation of lipophilic ion-pairs in these solvents. Here we wish to present discontinuous volume phase transition of &#039;super-absorbent&#039; ionic polymer gels the by change of solvent polarity even in low dielectric media. Moreover, we investigated the effect of neutral comonomers to swelling behaviours in various organic solvents by changing the length of their alkyl chains. The ionic polymer gels with longer alkyl chain swelled in a large magnitude in the less polar solvents and those with shorter alkyl one did in more polar solvents.

記述言語：その他  

Ionic polymer gels with the ability to absorb several hundreds times as much water as their dry weights have been used as &#039;super-absorbent polymers&#039; in wide range of biomedical and agricultural applications. However, in the low dielectric media (ε < 10), common ions form tightly bound ion-pairs or multiplet aggregates, and incompatibilities between the polymer chain and the solvents greatly diminish the swelling power. Here we report development of a new class of ionic polymer gels having lipophilic ion-pairs that consist of a lipophilic tetraphenylborate anion and a quaternary ammonium cation with long alkyl chains. They swelled largely in the less polar solvents such as tetrahydrofuran and chloroform as &#039;super-absorbent&#039; ionic polymer gels.

記述言語：その他  

Molecular design of polymer gels with high swelling properties in non polar solvents lays on compatibility of the polymer chain with oil. In this study, we demonstrate new polymer gels based on the hydrophobic ion pairs in the polymer chain. They provided the high swelling degrees in polar solvents. In the mixtures of water and acetonitrile, the polymer gels exhibited volume phase transition.

種別：査読等 

外国語雑誌　査読論文数：10

種別：大会・シンポジウム等 

参加者数：87

種別：大会・シンポジウム等 

種別：査読等 

外国語雑誌　査読論文数：3

種別：大会・シンポジウム等 

種別：大会・シンポジウム等 

参加者数：50

種別：大会・シンポジウム等 

種別：大会・シンポジウム等 

種別：大会・シンポジウム等 

参加者数：500

種別：大会・シンポジウム等