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

Abstract

Circularly polarized luminescence (CPL) dyes are recognized to be new generation materials and have been actively developed. Molecular recognition systems provide nice approaches to novel CPL materials, such as stimuli‐responsive switches and chemical sensing materials. CPL may be induced simply by mixing chiral or achiral, luminescent or nonluminescent host and guest; there are several combinations. Molecular recognition can potentially save time and effort to construct well‐ordered chiral structures with noncovalent attractive interactions as compared with the multi‐step synthesis of covalently bonded dyes. It is a challenging subject to engage molecular recognition events with CPL, and it is important and interesting to see how it is achieved. In fact, simple molecular recognition systems can even enable the fine adjustment of CPL performance and detailed conformational/configurational analysis of the excited state. Here we overview the recent achievements of simple host–guest complexes capable of exhibiting CPL, summarizing concisely the host/guest structures, CPL intensities, and characteristics.

DOI： 10.1002/chir.23522

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Other Link： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chir.23522

Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society ({ACS})  

DOI： 10.1021/acscatal.2c03583

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Carbazole-based aza[7]helicenes and hetero[9]helicenes were successfully obtained via the intramolecular Scholl reaction of 3,6-bis(biphenyl-2-yl)carbazole congeners, while the reaction of 3,6-bis(naphthylphenyl)-appended carbazole gave a triple helicene via an unexpected simultaneous double aryl rearrangement. DFT calculations suggested that the rearrangement proceeded via an arenium cation intermediate. In addition, the reaction of methoxy-appended substrate gave an azahepta[8]circulene via the concurrent C−C bond formation. These helical dyes showed circularly polarized luminescence. The azahepta[8]circulene was further transformed into deeply saddle-distorted dibenzodiaza[8]circulenes as the first example of its solution-based synthesis and unambiguous structural determination.

DOI： 10.1002/chem.202102269

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A variety of carbazolyl-appended Schiff bases were readily synthesized from 1-formylcarbazoles and aniline derivatives. Boron complexation of the resulting ligands allowed for facile preparation of new carbazole-based BODIPY analogues showing solid-state fluorescence. Furthermore, some dyes were converted into chiral compounds through the Et2 AlCl-mediated incorporation of a binaphthyl unit. The chiral dyes showed aggregation-induced fluorescence and circularly polarized luminescence (CPL) with the ΦF and glum of up to 0.22 and -3.5×10-3 , respectively, in the solid state. The solid-state fluorescence and CPL were well characterized by the crystal packing analyses and DFT calculations.

DOI： 10.1002/chem.202001463

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Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society (ACS)  

Hexameric and tetrameric porphyrin nanorings, Z6T6 and Z4T4, were synthesized in 53% and 14% yields, respectively, by the Sonogashira-type self-oligomerization of porphyrin monomer 1 using hexadentate template T6 and tetrapyridylporphyrin template T4. Template-free nanorings Z6 and Z4 were also prepared. The femtosecond transient absorption measurements revealed fast excitation energy hopping (EEH) along these nanorings with hopping rates of 2-5 ps. Treatment of Z6 with chiral template CT6 gave Z6CT6 showing circular dichroism (CD) and circularly polarized luminescence (CPL) in the absorption and fluorescence regions of Z6, respectively, which indicates chirality transfer from CT6 to Z6.

DOI： 10.1021/jacs.0c07707

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Bifunctional AlIII porphyrins with quaternary ammonium halides, 2-Cl and 2-Br, worked as excellent catalysts for the copolymerization of cyclohexene oxide (CHO) and CO2 at 120 °C. Turnover frequency (TOF) and turnover number (TON) reached 10 000 h-1 and 55 000, respectively, and poly(cyclohexene carbonate) (PCHC) with molecular weight of up to 281 000 was obtained with a catalyst loading of 0.001 mol%. In contrast, bifunctional MgII and ZnII counterparts, 3-Cl and 4-Cl, as well as a binary catalyst system, 1-Cl with bis(triphenylphosphine)iminium chloride (PPNCl), showed poor catalytic performances. Kinetic studies revealed that the reaction rate was first-order in [CHO] and [2-Br] and zero-order in [CO2], and the activation parameters were determined: ΔH‡ = 12.4 kcal mol-1, ΔS‡ = -26.1 cal mol-1 K-1, and ΔG‡ = 21.6 kcal mol-1 at 80 °C. Comparative DFT calculations on two model catalysts, AlIII complex 2' and MgII complex 3', allowed us to extract key factors in the catalytic behavior of the bifunctional AlIII catalyst. The high polymerization activity and carbonate-linkage selectivity originate from the cooperative actions of the metal center and the quaternary ammonium cation, both of which facilitate the epoxide-ring opening by the carbonate anion to form the carbonate linkage in the key transition state such as TS3b (ΔH‡ = 13.3 kcal mol-1, ΔS‡ = -3.1 cal mol-1 K-1, and ΔG‡ = 14.4 kcal mol-1 at 80 °C).

DOI： 10.1039/d0sc01609h

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Helical carbazole-based BODIPY analogues were readily synthesized via aza[7]helicenes. The structures of azahelicene-incorporated BF2 dyes were elucidated by x-ray diffraction analysis. DFT calculations revealed that the π-conjugated system expanded from the helicene moiety to the BODIPY framework. The azahelicene-fused boron complexes showed the Cotton effects and the circularly polarized luminescence (CPL) in the visible region. Furthermore, an axially chiral binaphthyl group was attached to the helically chiral dyes, which enhanced the chiroptical properties.

DOI： 10.1002/anie.202001186

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A series of carbazole-based boron dipyrromethenes (BODIPYs) 2 a-g bearing binaphthyl units have been synthesized by the Et2 AlCl-mediated reaction of the corresponding BODIPY difluorides 1 a-g with 1,1'-binaphthalene-2,2'-diol. Substituents such as halogen, nitrile, and amino groups were tolerated under the reaction conditions, and the reaction of the phenylethynyl-substituted 1 h gave (R,R)-3 h bearing two binaphthyl units. The chiroptical properties of these dyes with different substituents were investigated by UV/Vis, CD, fluorescence, and circularly polarized luminescence (CPL) spectroscopy. The CD spectra showed Cotton effects in the absorption region of the BODIPY moieties. In addition, they showed CPL both in solution and in the solid state. Interestingly, several dyes recorded higher glum values in the solid state, probably due to intermolecular interactions. Because (R,R)-3 h recorded relatively low glum values, the diastereomer (R,S)-3 h was prepared. The (R,S) diastereomer showed intense CPL, which suggests a synergetic effect of the two binaphthyl groups. Finally, chiral carbazole-based BODIPY dimers have been synthesized for the first time and their chiroptical properties were investigated. They showed redshifted fluorescence and CPL, which reached the near-IR (NIR) region in the solid state.

DOI： 10.1002/chem.201904954

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Authorship：Lead author   Publishing type：Research paper (scientific journal)   Publisher：World Scientific Pub Co Pte Lt  

Chiral carbazole-based porphyrins were synthesized for the first time via the incorporation of hydrobenzoin units at the thiophene moieties. They showed absorption and circular dichroism in the near-infrared (NIR) region. The NIR absorption was further red-shifted by solvent-induced aggregation.

DOI： 10.1142/s1088424619500937

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

<p>A highly conjugated carbazole-based fused diporphyrin shows NIR absorption.</p>

DOI： 10.1039/d0cc06289h

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Peripheral π-expansion of carbazole-based porphyrins was achieved for the first time by the Pt-catalyzed cyclization and the incorporation of a benzocarbazole unit. These two types of fused porphyrins showed red-shifted and broad NIR absorption due to the expanded π-conjugation as confirmed by NIR absorption spectroscopy and DFT calculations.

DOI： 10.1039/c9cc05079e

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Chiral binaphthyl-strapped Zn(II) porphyrins with triazolium halide units were synthesized as bifunctional catalysts for kinetic resolution of epoxides with CO2. Several catalysts were screened by changing the linker length and nucleophilic counteranions, and the optimized catalyst accelerated the enantioselective reaction at ambient temperature to produce optically active cyclic carbonates and epoxides.

DOI： 10.1021/acs.orglett.9b00447

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Chiral carbazole-based BODIPYs with a binaphthyl unit were synthesized via an Al-mediated reaction. Et2AlCl was found to be a convenient reagent for the reaction to give the chiral BODIPYs in high yields. It has been shown for the first time that these chiral carbazole-based BODIPYs show circularly polarized luminescence (CPL) both in solution and in the solid state.

DOI： 10.1039/c9cc00894b

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Doubly (R)-binaphthyl-strapped porphyrins with methylene chains were synthesized. The CD spectra showed the positive Cotton effect around the Soret bands, and several porphyrins showed CPL. In addition, we found that the chiral porphyrins were applicable to kinetic resolution of epoxide with CO2.

DOI： 10.1039/c8cc09114e

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

<p>
<italic>meso</italic>-Octamethylcalix[4]pyrrole worked as an organocatalyst for the conversion of epoxides and CO₂ into cyclic carbonates under solvent-free conditions.</p>

DOI： 10.1039/c8cy00941d

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Annulation reactions of the butadiyne-bridged carbazole dimer 1 produced carbazole-based chalcogenaisophlorins 2-4, which were transformed into the corresponding palladium complexes 2Pd-4Pd. The structures were characterized by NMR spectroscopy and X-ray diffraction analysis. Metallation fixed the structures which displayed weak antiaromatic character derived from the 20π isophlorin framework. These complexes showed weak near-infrared (NIR) absorption typical for antiaromatic porphyrinoids in solution. In addition, 2Pd and 3Pd showed relatively strong solid-state NIR absorption. X-ray diffraction analyses of 2Pd and 3Pd revealed trimeric and dimeric stacked layered structures, respectively, and DFT calculations suggest that the solid-state NIR absorption is ascribed to intermolecular charge transfer.

DOI： 10.1002/cplu.201700430

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

Carbazole-based BODIPY dimers 2a-g were synthesized via direct arylation. They showed red-shifted solid-state fluorescence spectra as compared with the corresponding monomer. In addition, unsymmetrical dimers 2d, 2f, and 2g with two different substituents showed red fluorescence with improved quantum yields in the solid state.

DOI： 10.1039/c7ob02419c

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Carbazole-based BODIPYs 1-6 with several different substituents at the boron atom site were synthesized. These dyes fluoresced in the solid state, and 3a with phenylethynyl groups exhibited a red-shifted and broad fluorescence spectrum, which suggested an excimer emission. Its derivatives 3b-n were synthesized, and the relationship between the solid-state emission and crystal packing was investigated. The X-ray crystal structures revealed cofacial dimers that might form excimers. From the structural optimization results, we found that the introduction of mesityl groups hindered intermolecular access and led to reduced interactions between the dimers. In addition, the red-shifted excimer fluorescence suppressed self-absorption, and dyes with ethynyl groups showed solid-state fluorescence in the vis/NIR region.

DOI： 10.1039/c7ob01473b

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The Glaser coupling reaction of ethynyl-substituted carbazole-based isophlorins provided butadiyne-bridged dimers, which were transformed into the thiophene-bridged dimers via the annulation reaction. Oxidation of these isophlorin dimers afforded carbazole-based diporphyrins. Notable electronic interactions in the diporphyrins have been confirmed by means of UV/vis-near-infrared (NIR) absorption spectroscopy, cyclic voltammetry (CV) measurements, and density functional theory (DFT) calculations.

DOI： 10.1021/acs.orglett.6b03054

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Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts.

DOI： 10.1002/tcr.201600053

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Language：Japanese   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

We developed various metalloporphyrins as bifunctional catalysts for the synthesis of cyclic carbonates from epoxides and CO2 under solvent-free conditions. The structures of the bifunctional catalysts were optimized step by step. As a result, a Zn porphyrin bearing eight nucleophiles at the meta positions showed a high turnover number (TON = 240,000) at 120 degrees C at 1.7 MPa CO2 and catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20 degrees C). Triporphyrin catalysts showed very high catalytic activity: TON = 220,000 and TOF = 46,000 h(-1) for the Mg triporphyrin, and TON = 310,000 and TOF= 40,000 for the Zn triporphyrin. The high catalytic activity of these bifunctional catalysts was due to the cooperative action of Mg2+ or Zn2+ and Br- and a conformational change (induced-fit) of the quaternary ammonium cation.

DOI： 10.5059/yukigoseikyokaishi.74.814

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DOI： 10.1021/jacs.6b06328

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Several carbazole-based boron dipyrromethene (BODIPY) dyes were synthesized by organometallic approaches. Thiazole, benzothiazole, imidazole, benzimidazole, triazole, and indolone substituents were introduced at the 1-position of the carbazole moiety, and boron complexation of each dipyrrin generated the corresponding compounds 1, 2 a, and 3-6. The properties of these products were investigated by UV/Vis and fluorescence spectroscopy, cyclic voltammetry, X-ray crystallography, and DFT calculations. These compounds exhibited large Stokes shifts, and compounds 1, 2 a, and 3-5 fluoresced both in solution and in the solid state. Complex 2 a showed the highest fluorescence quantum yield (ΦF ) in the solid state, therefore boron complexes of the carbazole-benzothiazole hybrids 2 b-f, which had several different substituents, were prepared and the effects of the substituents on the photophysical properties of the compounds were examined. The fluorescence properties showed good correlation with the results of crystal-packing analyses, and the dyes exhibited color-tunable solid-state fluorescence.

DOI： 10.1002/chem.201505150

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Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta, para, or ortho positions of meso-phenyl groups were synthesized as catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide under solvent-free conditions. The meta-substituted catalysts exhibited high catalytic performance, whereas the para- and ortho-substituted catalysts showed moderate and low activity, respectively. DFT calculations revealed the origin of the advantage of the meta-substituted catalyst, which could use the flexible quaternary ammonium cation at the meta position to stabilize various anionic species generated during catalysis. A zinc(II) porphyrin with eight nucleophiles at the meta positions showed very high catalytic activity (turnover number (TON)=240 000 at 120 °C, turnover frequency (TOF)=31 500 h(-1) at 170 °C) at an initial CO2 pressure of 1.7 MPa; catalyzed the reaction even at atmospheric CO2 pressure (balloon) at ambient temperature (20 °C); and was applicable to a broad range of substrates, including terminal and internal epoxides.

DOI： 10.1002/chem.201600164

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

The synthesis and photophysical properties of cyano and ethynyl substituted carbazole-based porphyrins were investigated. The introduction of ethynyl groups induced red shifts, while that of cyano groups induced blue shifts of their absorption bands, which was supported by MO calculations. Ethylenedioxy-appended porphyrins were also prepared via a coupling reaction. The conjugated and electronic substituent effects on the photophysical properties of the carbazole-based porphyrins have been elucidated by using both experimental results and calculations. Among these porphyrins, the ethylenedioxy-appended selenaporphyrin displayed intensified and red-shifted absorption in the NIR region up to 1178 nm.

DOI： 10.1039/c5ob01824b

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

Carbazole-based BODIPYs were synthesized in three steps using an organometallic approach consisting of sequential Ir-catalyzed borylation, Suzuki-Miyaura coupling, and boron complexation. Various substituents were introduced into the carbazole moiety, and large substituent effects were confirmed by means of absorption spectroscopy, cyclic voltammetry, and DFT calculations. Dibenzocarbazoles were also converted into the corresponding BODIPYs.

DOI： 10.1021/acs.orglett.5b01363

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO2 with epoxides to form cyclic carbonates, because of the multiple catalytic sites which cooperatively activate the epoxide. Catalytic activities were carefully investigated by controlling temperature, reaction time, and catalyst loading, and very high turnover number and turnover frequency were obtained: 220 000 and 46 000 h(-1) , respectively, for the magnesium catalyst, and 310 000 and 40 000 h(-1) , respectively, for the zinc catalyst. Results obtained with a zinc/free-base hybrid diporphyrin catalyst demonstrated that the Br(-) ions on the adjacent porphyrin moiety also function as nucleophiles.

DOI： 10.1002/anie.201409729

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We prepared bifunctional Mg(II) porphyrin catalysts 1 for the solvent-free synthesis of cyclic carbonates from epoxides and CO2. The activities of 1d, 1h, and 1i, which have Br(-), Cl(-), and I(-) counteranions, respectively, increased in the order 1i < 1h < 1d. Catalysts 1d and 1j-m, which bear four tetraalkylammonium bromide groups with different alkyl chain lengths, showed comparable but slightly different activities. Based on the excellent catalyst 1d, we synthesized Mg(II) porphyrin 1o with eight tetraalkylammonium bromide groups, which showed even higher catalytic activity (turnover number, 138,000; turnover frequency, 19,000 h(-1)). The catalytic mechanism was studied by using 1d. The yields were nearly constant at initial CO2 pressures in the 1-6 MPa range, suggesting that CO2 was not involved in the rate-determining step in this pressure range. No reaction proceeded in supercritical CO2, probably because the epoxide (into which the catalyst dissolved) dissolved in and was diluted by the supercritical CO2. Experiments with (18)O-labeled CO2 and D-labeled epoxide suggested that the catalytic cycle involved initial nucleophilic attack of Br(-) on the less hindered side of the epoxide to generate an oxyanion, which underwent CO2 insertion to afford a CO2 adduct; subsequent intramolecular ring closure formed the cyclic carbonate and regenerated the catalyst. Density functional theory calculations gave results consistent with the experimental results, revealing that the quaternary ammonium cation underwent conformational changes that stabilized various anionic species generated during the catalytic cycle. The high activity of 1d and 1o was due to the cooperative action of the Mg(II) and Br(-) and a conformational change (induced-fit) of the quaternary ammonium cation.

DOI： 10.1021/ja507665a

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Cu(I)-mediated annulation reaction of a 1,1'-(1,3-butadiyne)-8,8'-(2,5-thiophene)-bridged carbazole dimer 10 with amines provided the N-substituted carbazole-based isophlorines 11a-11c. A similar annulation reaction with selenium in the presence of hydrazine monohydrate afforded hetero-core-modified isophlorine 12. The oxidation of 12 generated the corresponding 21-selena-23-thiaporphyrin 13, which exhibited NIR absorption. The intramolecular charge transfer from Se to S was confirmed by the (1)H NMR results along with DFT calculations.

DOI： 10.1039/c3ob42564a

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Chemical fixation of carbon dioxide (CO2), which is an inexpensive and renewable carbon source, is becoming more and more important. The development of both new reactions and new catalysts is needed to overcome the kinetic and thermodynamic stability of CO2. Organic and metal catalysts with unique and excellent activity and selectivity have been developed for various chemical conversions of CO2. In this perspective, we provide an overview of the recent progress in this field, classifying it into several categories, where each research is concisely summarized one by one using a single reaction scheme, a representative catalyst structure, and/or a catalytic cycle.

DOI： 10.1039/c3cy00993a

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Several tetrakis(phenylethynyl)- and (phenylethynylphenylethynyl)-substituted carbazole-based thiaporphyrins were synthesized. These π-extended porphyrins display remarkably intensified and red-shifted absorption bands in the NIR region up to 1126 nm due to perturbation by the phenylethynyl substituents.

DOI： 10.1021/ol401403n

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DOI： 10.1002/chem.201202573

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

Cu(I)-mediated alkoxylation of doubly 1,3-butadiyne-bridged carbazole dimer 1, followed by acid-catalyzed cyclization, provided furan-bridged carbazole dimer 3, while annulation reaction of 1 with selenium in the presence of hydrazine monohydrate provided selenophene-bridged carbazole dimer 5a. Oxidation of isophlorin 5a afforded carbazole-based selenaporphyrin 5b, which possessed distinct aromaticity and produced intensified and red-shifted absorption bands in the near-IR region.

DOI： 10.1021/ol303392g

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The carbazole- and indolone-based porphyrinoids 3 and 4 were synthesized by stepwise transition-metal-catalyzed coupling reactions. Palladium metalation of 4 produced 4Pd, which exhibits near-infrared absorption.

DOI： 10.1021/ol300585v

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Peripherally ethynylated carbazole-based core-modified porphyrins were synthesized by sequential metal-catalyzed coupling and annulation reactions. Experimental results and DFT calculations both confirm that the p-conjugated networks of the resulting porphyrins effectively delocalize over the entire macrocycle, including the ethynyl substituent groups.

DOI： 10.1039/c2ob25645b

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It has been demonstrated that the direction and magnitude of transition dipole moments, and hence rates in the excitation energy hopping in the self-assembled porphyrin boxes can be tuned by insertion of ethynyl groups as well as the dielectric constant of solvent.

DOI： 10.1039/c2cc30834g

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DOI： 10.1002/chem.201100872

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DOI： 10.1002/anie.201101864

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DOI： 10.5517/ccwfzbl

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Other Link： http://orcid.org/0000-0002-0153-1888

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

meso-Triazolyl-appended Zn(II)-porphyrins were readily prepared by Cu(I)-catalyzed 1,3-dipolar cycloaddition of benzyl azide to meso-ethynylated Zn(II)-porphyrin (click chemistry). In noncoordinating CHCl(3) solvent, spontaneous assembly occurred to form tetrameric array (3)(2) from meso-meso-linked diporphyrins 3, and dodecameric porphyrin squares (4)(4) and (5)(4) from the L-shaped meso-meso-linked triporphyrins 4 and 5. The structures of these assemblies were examined by (1)H NMR spectra, absorption spectra, and their gel permeation chromatography (GPC) retention time. Furthermore, the structures of the dodecameric porphyrin squares (4)(4) and (5)(4) were probed by small- and wide-angle X-ray scattering (SAXS/WAXS) measurements in solution using a synchrotron source. Excitation-energy migration processes in these assemblies were also investigated in detail by using both steady-state and time-resolved spectroscopic methods, which revealed efficient excited-energy transfer (EET) between the meso-meso-linked Zn(II)-porphyrin units that occurred with time constants of 1.5 ps(-1) for (3)(2) and 8.8 ps(-1) for (5)(4).

DOI： 10.1002/chem.200903195

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Cu(I)-mediated annulation of meso,meso'-1,3-butadiyne-bridged Zn(II) diporphyrin with various amines efficiently provided meso,meso'-pyrrole-bridged Zn(II) diporphyrins. Notable intramolecular electronic interactions in these diporphyrins were observed. A starburst porphyrin pentamer was synthesized via Suzuki-Miyaura coupling of N-bromophenylpyrrole-bridged diporphyrin and meso,meso'-diborylated porphyrin.

DOI： 10.1021/ol100448x

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Cu(II)-catalyzed intramolecular cyclization of meso-(4-aminopyrid-3-yl)ethynyl Zn(II) porphyrin provided meso-(5-azaindol-2-yl)-substituted Zn(II) porphyrin. meso,meso'-Bis(5-azaindol-2-yl)-substituted diporphyrin 7 was similarly prepared and was found to form a fluorescent trimeric prismatic assembly consisting of single atropisomer 7(in-in).

DOI： 10.1021/ol902294r

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DOI： 10.1002/chem.200901475

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Cu(I)-catalyzed 1,3-dipolar cycloaddition of meso-ethynyl Zn(II) porphyrin with benzyl azide efficiently provides meso-1-benzyl-1H-1,2,3-triazolyl Zn(II) porphyrin, which assembles to form a slipped cofacial dimer by the complementary coordination of the triazole nitrogen atom at the 3-position to the zinc center of a second porphyrin moiety both in the solid and solution states. Removal of the benzyl protection and introduction of a 2-ethoxycarbonylphenyl moiety greatly stabilize the dimeric assembly through an additional hydrogen bonding interaction between the NH proton of 2H-1,2,3-triazole and the carbonyl oxygen.

DOI： 10.1021/ol7028299

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Language：English   Publisher：ELSEVIER SCIENCE SA  

We have explored a variety of self-assembled cyclic porphyrin arrays mainly as biomimetic models of light harvesting antenna in photosynthetic systems. The key reaction is Ag(I)-promoted coupling reaction of 5,15-diaryl zinc(II) porphyrin that provides a meso-meso linked diporphyrin. meso-Pyridine-appended zinc(II) porphyrins M1-M3 and their meso-meso linked dimers D1-D3 assemble spontaneously in non-coordinating solvents into tetrameric porphyrin squares S1-S3 and porphyrin boxes B1-B3, respectively. In the latter case, it has been demonstrated that four molecules of R-diporphyrin assemble into R-box and four molecules of S-diporphyrin assemble into S-box via rigorous homochiral self-sorting process. Efficient excitation energy transfer along these cyclic porphyrin arrays has been revealed by the time-resolved transient absorption and fluorescence measurements. We have also demonstrated that the meso-cinchomeronimide appended Zn(II) porphyrin CIM forms a cyclic trimer, while the corresponding diporphyrins CID exhibit high-fidelity self-sorting assembling to form discrete cyclic trimer, tetramer, and pentamer with large association constants, through perfect discrimination of enantiomeric and conformational differences of the meso-cinchomeronimide substituents. (C) 2007 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ccr.2007.02.017

Web of Science

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

Pd-catalyzed annulation reaction of meso-hexynyl Zn(II) porphyrin with 4-amino-3-iodopyridine efficiently provides meso-3-(5-azaindolyl)-substituted Zn(II) porphyrin as a major product, which assembles to form a slipped cofacial dimer by the complementary coordination of the pyridine moiety to the Zn(II) center. 2-iodoaniline and 2-iodophenol also undergo this [3 + 2] annulation with the meso-hexynyl Zn(II) porphyrin to furnish meso-indolyl- and benzofuranyl-substituted Zn(II) porphyrins, respectively.

DOI： 10.1021/ol070885k

Web of Science

PubMed

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

Treatment of various hydroquinones and catechols with meso-pentafluorophenyl [26]hexaphyrin(1.1.1.1.1.1) provided the corresponding quinones quantitatively.

DOI： 10.1039/b515740d

Web of Science

PubMed

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Event date： 2019.10.15

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2019.9.26

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：大阪  

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Event date： 2019.9.26

Language：Japanese   Presentation type：Poster presentation  

Venue：大阪  

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Event date： 2019.9.26

Language：Japanese   Presentation type：Poster presentation  

Venue：大阪  

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Event date： 2019.9.25

Language：Japanese   Presentation type：Poster presentation  

Venue：大阪  

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Event date： 2019.9.25

Language：Japanese   Presentation type：Poster presentation  

Venue：大阪  

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Event date： 2019.9.3

Language：Japanese   Presentation type：Poster presentation  

Venue：松江  

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Event date： 2019.9.3

Language：Japanese   Presentation type：Poster presentation  

Venue：松江  

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Event date： 2019.7.23

Language：English   Presentation type：Poster presentation  

Venue：Sapporo  

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Event date： 2019.7.22

Language：English   Presentation type：Poster presentation  

Venue：Sapporo  

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Event date： 2019.7.22

Language：English   Presentation type：Poster presentation  

Venue：Sapporo  

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Event date： 2019.6.15

Language：Japanese   Presentation type：Poster presentation  

Venue：金沢  

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Event date： 2019.6.15

Language：Japanese   Presentation type：Poster presentation  

Venue：金沢  

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Event date： 2019.6.14

Language：Japanese   Presentation type：Poster presentation  

Venue：金沢  

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Event date： 2019.6.3

Language：English   Presentation type：Poster presentation  

Venue：Nara  

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Event date： 2019.5.30

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：Dallas, USA  

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Event date： 2019.5.18

Language：Japanese   Presentation type：Poster presentation  

Venue：金沢  

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Event date： 2019.3.17

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：神戸  

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Event date： 2019.3.17

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：神戸  

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Event date： 2019.3.17

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：神戸  

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Event date： 2019.3.17

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：神戸  

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Event date： 2019.3.16

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：神戸  

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Event date： 2018.11.30

Language：Japanese   Presentation type：Poster presentation  

Venue：高島  

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Event date： 2018.11.30

Language：Japanese   Presentation type：Poster presentation  

Venue：高島  

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Event date： 2018.11.17

Language：Japanese   Presentation type：Poster presentation  

Venue：松山  

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Event date： 2018.11.17

Language：Japanese   Presentation type：Poster presentation  

Venue：松山  

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Event date： 2018.11.17

Language：Japanese   Presentation type：Poster presentation  

Venue：松山  

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Event date： 2018.11.17

Language：Japanese   Presentation type：Poster presentation  

Venue：松山  

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Event date： 2018.9.13

Language：Japanese   Presentation type：Poster presentation  

Venue：高知  

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Event date： 2018.9.13

Language：Japanese   Presentation type：Poster presentation  

Venue：高知  

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Event date： 2018.9.10

Language：English   Presentation type：Poster presentation  

Venue：大阪  

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Event date： 2018.9.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：大阪  

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Event date： 2018.9.7

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2018.9.7

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2018.9.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東京  

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Event date： 2018.9.6

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2018.9.6

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2018.8.4

Language：English   Presentation type：Oral presentation (general)  

Venue：仙台  

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Event date： 2018.7.3

Language：English   Presentation type：Oral presentation (general)  

Venue：ミュンヘン  

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Event date： 2018.7.2

Language：English   Presentation type：Oral presentation (general)  

Venue：ミュンヘン  

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Event date： 2018.6.16

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：草津  

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Event date： 2018.6.16

Language：English   Presentation type：Poster presentation  

Venue：草津  

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Event date： 2018.6.6

Language：Japanese   Presentation type：Poster presentation  

Venue：名古屋  

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Event date： 2018.6.6

Language：Japanese   Presentation type：Poster presentation  

Venue：名古屋  

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Event date： 2018.6.6

Language：Japanese   Presentation type：Poster presentation  

Venue：名古屋  

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Event date： 2018.6.2

Language：Japanese   Presentation type：Poster presentation  

Venue：野田  

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Event date： 2018.6.2

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：野田  

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Event date： 2018.5.13

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：Seattle, USA  

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Event date： 2018.3.23

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.22

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.22

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.22

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.20

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.20

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.20

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.20

Language：English   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.20

Language：English   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.20

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2018.3.20

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：船橋  

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Event date： 2017.12.15

Language：Japanese   Presentation type：Poster presentation  

Venue：秩父  

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Event date： 2017.12.14

Language：English   Presentation type：Poster presentation  

Venue：宇治  

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Event date： 2017.12.8

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2017.12.8

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2017.11.11

Language：Japanese   Presentation type：Poster presentation  

Venue：鳥取  

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Event date： 2017.11.11

Language：Japanese   Presentation type：Poster presentation  

Venue：鳥取  

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Event date： 2017.11.11

Language：Japanese   Presentation type：Poster presentation  

Venue：鳥取  

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Event date： 2017.9.8

Language：Japanese   Presentation type：Poster presentation  

Venue：福岡  

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Event date： 2017.9.7

Language：Japanese   Presentation type：Poster presentation  

Venue：福岡  

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Event date： 2017.9.7

Language：Japanese   Presentation type：Poster presentation  

Venue：福岡  

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Event date： 2017.9.7

Language：Japanese   Presentation type：Poster presentation  

Venue：福岡  

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Event date： 2017.9.7

Language：Japanese   Presentation type：Poster presentation  

Venue：福岡  

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Event date： 2017.9.1

Language：Japanese   Presentation type：Poster presentation  

Venue：鳥取  

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Event date： 2017.9.1

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：鳥取  

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Event date： 2017.9.1

Language：Japanese   Presentation type：Poster presentation  

Venue：鳥取  

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Event date： 2017.9.1

Language：Japanese   Presentation type：Poster presentation  

Venue：鳥取  

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Event date： 2017.8.26

Language：Japanese   Presentation type：Oral presentation (invited, special)  

Venue：鳥取  

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Event date： 2017.7.11

Language：English   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2017.7.10

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2017.6.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：岡山  

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Event date： 2017.6.8

Language：Japanese   Presentation type：Poster presentation  

Venue：岡山  

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Event date： 2017.6.8

Language：Japanese   Presentation type：Poster presentation  

Venue：岡山  

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Event date： 2017.6.3

Language：Japanese   Presentation type：Poster presentation  

Venue：草津  

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Event date： 2017.6.3

Language：Japanese   Presentation type：Poster presentation  

Venue：草津  

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Event date： 2017.6.2

Language：Japanese   Presentation type：Poster presentation  

Venue：草津  

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Event date： 2017.5.12

Language：English   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2017.3.19

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2017.3.19

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2017.3.18

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2017.3.18

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2017.3.18

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2017.3.18

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2016.12.16

Language：Japanese   Presentation type：Poster presentation  

Venue：京都  

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Event date： 2016.11.16

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2016.11.16

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2016.11.16

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2016.11.11

Language：Japanese   Presentation type：Poster presentation  

Venue：東京  

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Event date： 2016.11.5

Language：Japanese   Presentation type：Poster presentation  

Venue：高松  

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Event date： 2016.11.5

Language：Japanese   Presentation type：Poster presentation  

Venue：高松  

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Event date： 2016.9.8

Language：Japanese   Presentation type：Poster presentation  

Venue：金沢  

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Event date： 2016.9.6

Language：Japanese   Presentation type：Poster presentation  

Venue：ニセコ  

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Event date： 2016.9.2

Language：Japanese   Presentation type：Poster presentation  

Venue：広島  

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Event date： 2016.9.2

Language：Japanese   Presentation type：Poster presentation  

Venue：広島  

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Event date： 2016.9.1

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：広島  

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Event date： 2016.9.1

Language：Japanese   Presentation type：Poster presentation  

Venue：広島  

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Event date： 2016.7.7

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：Nanjing, China  

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Event date： 2016.6.5

Language：Japanese   Presentation type：Poster presentation  

Venue：高知  

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Event date： 2016.6.4

Language：Japanese   Presentation type：Poster presentation  

Venue：高知  

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Event date： 2016.6.4

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：高知  

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Event date： 2016.5.31

Language：English   Presentation type：Oral presentation (invited, special)  

Venue：San Diego, USA  

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Event date： 2016.4.22

Language：English   Presentation type：Poster presentation  

Venue：大阪  

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Event date： 2016.3.27

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2016.3.27

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2016.3.27

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2016.3.25

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2016.3.25

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2016.3.24

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2016.3.24

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2016.3.24

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京田辺  

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Event date： 2013.6.24 - 2013.6.28

Language：English   Presentation type：Oral presentation (general)  

Venue：Cheju, Korea  

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Event date： 2013.3.22 - 2013.3.25

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：草津  

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Event date： 2013.3.3 - 2013.3.7

Language：English   Presentation type：Poster presentation  

Venue：Sorrento, Italy  

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Event date： 2012.9.19 - 2012.9.21

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京都  

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Event date： 2012.7.1 - 2012.7.6

Language：English   Presentation type：Poster presentation  

Venue：Cheju, Korea  

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Event date： 2012.3.25 - 2012.3.28

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2011.9.21 - 2011.9.23

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：つくば  

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Event date： 2011.9.17 - 2011.9.19

Language：Japanese   Presentation type：Poster presentation  

Venue：岡山  

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Event date： 2011.7.24 - 2011.7.29

Language：English   Presentation type：Poster presentation  

Venue：Eugene, USA  

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Event date： 2011.3.26 - 2011.3.29

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜  

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Event date： 2010.12.15 - 2010.12.20

Language：English   Presentation type：Poster presentation  

Venue：Honolulu, USA  

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Event date： 2010.6.6 - 2010.6.10

Language：English   Presentation type：Poster presentation  

Venue：Nara  

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