Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：World Scientific Pub Co Pte Ltd  

Cyclo[8]pyrrole–phosphonate complexes were synthesized via the anion exchange method from cyclo[8]pyrrole sulfate. The molecular structures were determined by X-ray diffraction studies.

DOI： 10.1142/s1088424623500438

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

DOI： 10.1021/acs.joc.3c00196

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：World Scientific Pub Co Pte Ltd  

DOI： 10.1142/s1088424623500980

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

DOI： 10.1021/acs.orglett.3c00876

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Japan Institute of Heterocyclic Chemistry  

DOI： 10.3987/COM-23-14826

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：World Scientific Pub Co Pte Ltd  

Bicyclo[2.2.2]octadiene(BCOD)-fused 5,15-diazaporphyrins were synthesized via a metal-template aza-annulation of dipyrrin-metal complexes as a soluble precursor of tetrabenzodiazaporphyrin. 10-Azacorrole copper complex with a meso-imine bridge was serendipitously obtained via the same reaction using dimethylBCOD-fused dipyrrin-copper complex.

DOI： 10.1142/s1088424623500074

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

Dibenzofurans featuring a 2,2'-biazulene framework were prepared in good yields by Brønsted acid-promoted annulation of 2,3-di(1-azulenyl)benzofurans in 100% H3PO4. The NMR, UV-Vis, and fluorescent spectroscopies were used to investigate the...

DOI： 10.1039/d3cc00373f

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Authorship：Last author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：World Scientific Pub Co Pte Ltd  

DOI： 10.1142/s1088424622500900

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Starting with the reaction of 2H-cyclohepta[b]furan-2-ones with an enamine, which was prepared from 4-tert-butylcyclohexanone and pyrrolidine, benz[a]azulenes having both formyl and tert-butyl groups were obtained in the three-step sequence. Subsequently, both the formyl and tert-butyl groups were eliminated by heating the benz[a]azulene derivatives in 100% H3PO4 to give benz[a]azulenes without these substituents in high yields. In terms of product yield, this method is the best one ever reported for the synthesis of the parent benz[a]azulene so far. The conversion of the benz[a]azulene derivatives with a formyl group into cyclohept[a]acenaphthylen-3-one derivatives was also investigated via Knoevenagel condensation with dimethyl malonate, followed by Brønsted acid-mediated intramolecular cyclization. The structural features including the bond alternation in the benz[a]azulene derivatives were revealed by NMR studies, NICS calculations, and a single-crystal X-ray structural analysis. The optical and electrochemical properties of a series of benz[a]azulene derivatives were evaluated by UV/Vis, fluorescence spectroscopy, and voltammetry experiments. As a result, we found that some benz[a]azulene derivatives showed remarkable luminescence in acidic media. In addition, the benz[a]azulene derivatives with the electron-withdrawing group and cyclohept[a]acenaphthylen-3-one derivative displayed good reversibility in the spectral changes under the electrochemical redox conditions.

DOI： 10.1021/acs.joc.2c00133

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

Starting with the reaction of 2H-cyclohepta[b]-furan-2-ones with an enamine, which was prepared from 4-tert-butylcyclohexanone and pyrrolidine, benz[a]azulenes having bothformyl andtert-butyl groups were obtained in the three-stepsequence. Subsequently, both the formyl andtert-butyl groups wereeliminated by heating the benz[a]azulene derivatives in 100% H3PO4to give benz[a]azulenes without these substituents in highyields. In terms of product yield, this method is the best one ever reported for the synthesis of the parent benz[a]azulene so far. Theconversion of the benz[a]azulene derivatives with a formyl group into cyclohept[a]acenaphthylen-3-one derivatives was alsoinvestigatedviaKnoevenagel condensation with dimethyl malonate, followed by Bronsted acid-mediated intramolecular cyclization.The structural features including the bond alternation in the benz[a]azulene derivatives were revealed by NMR studies, NICScalculations, and a single-crystal X-ray structural analysis. The optical and electrochemical properties of a series of benz[a]azulenederivatives were evaluated by UV/Vis,fluorescence spectroscopy, and voltammetry experiments. As a result, we found that somebenz[a]azulene derivatives showed remarkable luminescence in acidic media. In addition, the benz[a]azulene derivatives with theelectron-withdrawing group and cyclohept[a]acenaphthylen-3-one derivative displayed good reversibility in the spectral changes under the electrochemical redox conditions.

DOI： 10.1021/acs.joc.2c00133

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

The synthesis of 8-aryl-2H-cyclohepta[b]furan-2-ones was accomplished by the Suzuki-Miyaura coupling of arylboronic acids with the triflates prepared from an 8-hydroxy-2H-cyclohepta[b]furan-2-one derivative. The 8-aryl-2H-cyclohepta[b]furan-2-ones were converted to 4-arylazulenes via an [8 + 2] cycloaddition reaction with the enamine prepared from acetaldehyde and diethylamine. The optical properties of 4-arylazulenes were characterized by UV/Vis and fluorescence spectra.

DOI： 10.1246/cl.220076

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

Tropo(thio)ne-embedded homoHPHACs and their dications were synthesised by an electrophilic annulation of secoHPHAC and successive oxidation. 13C NMR spectra of the dications represented global 22π homoaromaticity via homoconjugation, while alkylation...

DOI： 10.1039/d1cc07152a

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

A “3+3” condensation reaction of 1,3-di(2-pyrrolyl)azulene with aryl aldehyde followed by an oxidative aromatization afforded diazuliamethyrin, [24]diazulihexaphyrin(0.1.0.0.1.0). X-ray diffraction analysis revealed a relatively planar structure of diprotonated diazuliamethyrin with a mean plane deviation of 0.37 Å. A 24π non- or antiaromatic character was confirmed by 1H NMR, absorption, MCD spectra, and TD-DFT calculations that included the NICS values and ACID plots.

DOI： 10.1021/acs.orglett.1c03882

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Bicyclo[2.2.2]octadiene(BCOD)-fused dithiaamethyrin 4 was synthesized via a "3+3"condensation method. Thermal conversion of the BCOD moieties afforded tetrabenzodithiaamethyrin 5. The highly planar structures of 4 and 5 were confirmed by X-ray diffraction studies. The 1H NMR, absorption and MCD spectra, together with TD-DFT calculations revealed that both BCOD-fused and -extended dithiaamethyrins have a 24 antiaromatic character.

DOI： 10.1142/S1088424621500966

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Cyclo[9]pyrrole, a ring-expanded porphyrin without meso-bridges and having an odd number of pyrroles, was synthesized via the oxidative coupling of 2,2′:5′,2″-terpyrrole. X-ray crystallography showed a C2-like symmetry with a large root-mean-square deviation. The optical properties and electronic structures were analyzed using magnetic circular dichroism spectroscopy and time-dependent density functional theory calculations.

DOI： 10.1021/acs.orglett.1c00899

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

Symmetrical octaphenyltetrabenzoporphyrins 3 were synthesized via cyclotetramerization from bicyclo[2.2.2]octadiene (BCOD)-fused pyrrole, followed by a thermal conversion based on retro DielsAlder reaction. X-ray diffraction analysis revealed that the zinc complex 3b had C4h symmetry.

DOI： 10.1246/cl.210045

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

DOI： 10.1021/acs.joc.0c02825

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

DOI： 10.1021/acs.nanolett.0c03510

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

Azulene derivatives with heterocyclic moieties in the molecule have been synthesized for applications in materials science by taking advantage of their unique properties. These derivatives have been prepared by various methods, involving electrophilic substitution, condensation, cyclization, and transition metal-catalyzed cross-coupling reactions. Herein, we present the development of the synthetic methods, reactivities, and physical properties for the heterocycle-substituted and heterocycle-fused azulenes reported in the last decade.

DOI： 10.3390/ijms21197087

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

A bicyclo[2.2.2]octadiene(BCOD)-fused bis(dipyrromethane) derivative was reacted with methylal in the presence of trifluoroacetic acid followed by oxidation with chloranil to give a doubly N-confused phlorin derivative, which did not undergo the retro-Diels–Alder reaction extruding an ethylene molecule on heating. In contrast, a 7-tert-butoxybicyclo[2.2.1]heptadiene(7-BuOBCHD)-fused bis(dipyrromethane) yielded benzene-ring-fused doubly N-confused porphyrins by following similar reaction sequences.

DOI： 10.1002/chem.202000339

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Other Link： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202000339

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

A ring-contracted carbaporphyrin, azulitriphyrin(2.1.1), was synthesized via intramolecular McMurry coupling reaction. Absorption, NMR spectra and NICS calculations of protonated azulitriphyrin(2.1.1) revealed its Hückel aromatic character as a 14[Formula: see text] porphyrinoid.

DOI： 10.1142/s108842461950130x

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In this paper, we describe an efficient and atom-economical synthesis of highly functionalized pyrroles, pentafulvenes, and pyrrolopyridines by [2+2] cycloaddition-retroelectrocyclization of N-substituted propargylamines with tetracyanoethylene, followed by the treatment of the resulting tetracyanobutadiene derivatives with silica gel. In this reaction, silica gel plays an important role to promote the intramolecular cyclization to afford the heterocyclic products from the tetracyanobutadiene intermediates. The products were obtained selectively depending on the substituent on the nitrogen atom of the starting propargylamines.

DOI： 10.1002/chem.201904926

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Authorship：Lead author,　Corresponding author   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/bcsj.20190074

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© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim A series of free-base and phosphorus(V) complexes of tetrabenzoporphyrin (TBP) and some phosphorus(V) porphyrins containing four or eight phenyl groups on the periphery have been synthesized and characterized by X-ray crystallography, electronic absorption, and magnetic circular dichroism (MCD) spectroscopy, together with quantum chemical calculations. All phosphorus TBP and meso-tetraphenyl porphyrin complexes adapted ruffled conformations due to the small P(V) ion, although the Zn(II)TBPs containing eight phenyl (Φ) groups at the so-called β and α positions showed planar and saddled structures in the solid state, due to, respectively, marginal or severe steric hindrance between the neighboring Φ groups. All P(V)TBPs showed the Soret and Q bands beyond 450 and 700 nm, respectively, which are some of the longest wavelengths exhibited by metallated TBPs reported to date. Of the eight Φ group-substituted P(V)TBPs, those substituted at α positions always showed absorption bands at longer wavelengths than those at β positions, which was reproduced by calculated absorption spectra. The Soret band positions of meso-tetraphenylated P(V) species without fused benzo-groups (ca. 430–440 nm) were also some of the longest among metalloporphyrins of this type.

DOI： 10.1002/ejoc.201900528

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

<p>The reaction of several azulenylalkynes having an aryl substituent with elemental sulfur afforded the corresponding azuleno[2,1-b]thiophenes in good yields.</p>

DOI： 10.1039/c9qo00593e

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Authorship：Lead author,　Corresponding author   Publishing type：Research paper (scientific journal)   Publisher：Japan Institute of Heterocyclic Chemistry  

DOI： 10.3987/com-18-s(f)102

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© 2019 The Chemical Society of Japan Di(acenaphtho)-fused BODIPYs with four electron-withdrawing N,N-dimethylcarbamoyl groups were obtained by complexation of the corresponding dipyrrins, which were also proven to be a stable deep-red dye.

DOI： 10.1246/bcsj.20190021

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

<p>The reaction of 1,2-diformylazulene with maleimides in the presence of PPh₃ gave the azulenophthalimides. The optical and electrochemical properties of the azulenophthalimides were investigated.</p>

DOI： 10.1039/c8qo01121d

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Copyright © 2018 American Chemical Society. A core-expanded, pyrrole-fused azacoronene analogue containing two unusual N-doped heptagons was obtained from commercially available octafluoronaphthalene and 3,4-diethylpyrrole in two steps as a heteroatom-doped nonplanar nanographene. Full fusion with the formation of the tetraazadipleiadiene framework and the longitudinally twisted structure was unambiguously confirmed by single-crystal X-ray diffraction analysis. The edge-to-edge dihedral angle along the acene moiety was 63°. This electron-rich π-system showed four reversible oxidation peaks. Despite the nonplanar structure, the Hückel aromaticity owing to a peripheral π-conjugation in the dicationic state was concluded from the bond-length alternation and nucleus-independent chemical shift (NICS) and anisotropy of the induced current density (ACID) calculations.

DOI： 10.1021/jacs.8b06079

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© 2018 The Japan Institute of Heterocyclic Chemistry – 3-Substituted 2-amino-1-cyanoazulene derivatives were prepared by the reaction of 2H-cyclohepta[b]furan-2-ones with malononitrile in the presence of triethylamine as a base. The great influence of the substituent at their 3-position on the reactivity to form the 2-aminoazulene derivatives was revealed. The intramolecular charge transfer (ICT) characters of 2-amino-1-cyano-3-vinylazulenes were investigated by UV/Vis spectroscopy and theoretical calculations. The structure of compounds 13b and 14b was clarified by single crystal X-ray analysis.

DOI： 10.3987/COM-18-S(T)89

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Authorship：Lead author,　Corresponding author   Publishing type：Research paper (scientific journal)   Publisher：Japan Institute of Heterocyclic Chemistry  

DOI： 10.3987/com-18-13910

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© 2018 The Royal Society of Chemistry. Benzene-fused bis(acenaphthoBODIPY)s prepared by retro-Diels-Alder reaction of bicyclo[2.2.2]octadiene-fused precursors showed strong absorption bands in the near-infrared region and very weak absorptions in the visible region.

DOI： 10.1039/c8ra01694a

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Controlling the structural deformation of organic molecules can drive unique reactions that cannot be induced only by thermal, optical or electrochemical procedures. However, in conventional organic synthesis, including mechanochemical procedures, it is difficult to control skeletal rearrangement in polycyclic aromatic hydrocarbons (PAHs). Here, we demonstrate a reaction scheme for the skeletal rearrangement of PAHs on a metal surface using high-resolution noncontact atomic force microscopy. By a combination of organic synthesis and on-surface cyclodehydrogenation, we produce a well-designed PAH - diazuleno[1,2,3-cd:1′,2′,3′-fg]pyrene - adsorbed flatly onto Cu(001), in which two azuleno moieties are highly strained by their mutual proximity. This local strain drives the rearrangement of one of the azuleno moieties into a fulvaleno moiety, which has never been reported so far. Our proposed thermally driven, strain-induced synthesis on surfaces will pave the way for the production of a new class of nanocarbon materials that conventional synthetic techniques cannot attain.

DOI： 10.1038/ncomms16089

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The SNAr reaction of 2-chloroazulene derivative 1 with ethoxycarbonyl groups at the 1,3-positions of the azulene ring with several amines afforded the corresponding 2-aminoazulenes 3-9 in excellent yields. 2-Chloroazulene (2) without the electron-withdrawing groups reacted with highly nucleophilic cyclic amines (i.e., morpholine, piperidine and pyrrolidine) under the high-temperature conditions in a sealed tube to produce the corresponding 2-aminoazulenes 10-12 in good yields. 2-Aminoazulenes 10-14 without the electron-withdrawing groups were also obtained in good yields by the treatment of compounds 3-7 with 100% H3PO4, but in the cases of the reaction of 8 and 9 with a secondary amine function, the decomposition of the products resulted. The synthesis of 2-arylazoazulenes 15-18 was also established via the SNAr reaction of 1 with arylhydrazines. The optical and electrochemical properties of the 2-arylazoazulene derivatives were examined by UV/Vis spectroscopy, theoretical calculations and voltammetric experiments.

DOI： 10.1039/c7ob00691h

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The SNAr reaction of 2-chloroazulene derivative 1 with ethoxycarbonyl groups at the 1,3-positions of the azulene ring with several amines afforded the corresponding 2-aminoazulenes 3-9 in excellent yields. 2-Chloroazulene (2) without the electron-withdrawing groups reacted with highly nucleophilic cyclic amines (i.e., morpholine, piperidine and pyrrolidine) under the high-temperature conditions in a sealed tube to produce the corresponding 2-aminoazulenes 10-12 in good yields. 2-Aminoazulenes 10-14 without the electron-withdrawing groups were also obtained in good yields by the treatment of compounds 3-7 with 100% H3PO4, but in the cases of the reaction of 8 and 9 with a secondary amine function, the decomposition of the products resulted. The synthesis of 2-arylazoazulenes 15-18 was also established via the SNAr reaction of 1 with arylhydrazines. The optical and electrochemical properties of the 2-arylazoazulene derivatives were examined by UV/Vis spectroscopy, theoretical calculations and voltammetric experiments.

DOI： 10.1039/c7ob00691h

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Synthesis of 2-aminofuran derivatives with an azulene or N,N-dimethylanilino substituent was established by the formal [2+2] cycloaddition-retroelectrocyclization of 3-(1-azulenyl or N,N-dimethylanilino)-2-propyn-1-ols with tetracyanoethylene, followed by intramolecular nucleophilic addition to the initially formed tetracyanobutadiene moiety of the internal hydroxyl group that come from 2-propyn-1-ol. The reaction proceeds under mild conditions with short reaction period. The products of the reaction are readily available through a simple purification procedure. 2-Aminofuran derivatives obtained by this reaction could be converted into 6-aminofulvene derivatives upon reaction with various amines. The structures of 2-aminofuran and 6-aminopentafulvene with a N,N-dimethylanilino substituent were confirmed by single-crystal X-ray structural analysis.

DOI： 10.1002/chem.201700121

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Tetrathiafulvalene (TTF) derivatives with 2-azulenyl substituents 5-11 were prepared by the palladium-catalyzed direct arylation reaction of 2-chloroazulenes with TTF in good yield. Photophysical properties of these compounds were investigated by UV-vis spectroscopy and theoretical calculations. Redox behavior of the novel azulene-substituted TTFs was examined by using cyclic voltammetry and differential pulse voltammetry, which revealed their multistep electrochemical oxidation and/or reduction properties. Moreover, these TTF derivatives showed significant spectral change in the visible region under the redox conditions.

DOI： 10.1021/acs.joc.6b02818

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

A cyclophane composed of diethanoanthracene (DEA)-fused dipyrrole and tetrafluorobenzene was synthesized by one-pot aromatic nucleophilic substitution (SNAr). Reflecting the fixed angle of DEA-fused dipyrrole, X-ray single-crystal structure analysis of the cyclophane revealed its rice-ball-shaped structure.

DOI： 10.1246/cl.161026

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Parikh-Doering oxidation of diethyl 9-hydroxy-2,6-dimethy1-4,8-dihydro-4,8-methanopyrrol[3,4-f]isoindole-1,7-dicarboxylate produced diethyl 9-oxo-2,6-dimethy1-4,8-dihydro-4,8-methanopyrrol[3,44] isoindole-1,7-dicarboxylate. This carbonyl derivative spontaneously underwent cheletropic extrusion of carbon monoxide, producing diethyl 2,6-dimethylpyrrol[3,4-f]isoindole-1,7-dicarboxylate, which showed 14 pi-electronic aromaticity on the whole five-six-five ring system. (C) 2017 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2017.01.015

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The protonation behavior of bicyclo[2.2.2]octadiene (BCOD)-fused thiaporphyrin and thiabenzoporphyrin was examined by titration with trifluoroacetic acid. Neutral, monorotonated, and diprotonated species of thiaporphyrins were easily detected by UV-vis spectral measurement. The first (K-1) and second (K-2) equilibrium constants were found to be K-1 = 520 and K-2 approximate to 7.1 for BCOD-fused thiaporphyrin and K-1 = 1.4 x 10(4) and K-2 approximate to 1.4 for thiabenzoporphyrin. The difference between K-1 and K-2 values of thiaporphyrins is larger than that observed for porphyrins (N-4-porphyrins). The main contributing conjugation pathways for thiaporphyrins in both protonated species were investigated by NICS and AICD quantum calculations using their atomic geometries obtained by X-ray structural analysis. The 18 pi-conjugation pathways of the neutral, monoprotonated, and diprotonated species thiaporphyrins were found to contain 18, 19, and 20 atoms, respectively. Results of H-1 NMR studies also support the major contributing pathways. (C) 2016 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2016.12.067

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Parikh-Doering oxidation of diethyl 9-hydroxy-2,6-dimethy1-4,8-dihydro-4,8-methanopyrrol[3,4-f]isoindole-1,7-dicarboxylate produced diethyl 9-oxo-2,6-dimethy1-4,8-dihydro-4,8-methanopyrrol[3,44] isoindole-1,7-dicarboxylate. This carbonyl derivative spontaneously underwent cheletropic extrusion of carbon monoxide, producing diethyl 2,6-dimethylpyrrol[3,4-f]isoindole-1,7-dicarboxylate, which showed 14 pi-electronic aromaticity on the whole five-six-five ring system. (C) 2017 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2017.01.015

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DOI： 10.3987/COM-16-S(S)25

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

In this study, a benzene-fused bis(thiaporphyrin) was synthesized by the retro-DielsAlder reaction of a bicyclo[2.2.2]- octadiene (BCOD)-fused bis(thiaporphyrin) precursor. This precursor was prepared by the double [3+1] porphyrin synthesis of the BCOD-fused dipyrrole with thiatripyrrane. The ultravioletvisible (UVvis) spectrum of benzene-fused bis- (thiaporphyrin) in dichloromethane was extremely different from that of the corresponding benzene-fused bis(porphyrin). In contrast, extremely similar spectra were obtained in the presence of trifluoroacetic acid. The similar electronic structures in the protonated states were supported by X-ray analysis and time-dependent density-functional theory (TD-DFT) calculations.

DOI： 10.1246/bcsj.20170257

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© 2017 The Japan Institute of Heterocyclic Chemistry. Tetraarylpyrroles with a 1-azulenyl substituent were prepared by the reaction of 1-azulenyl ketones, which have various aryl-substituents at their á-position, with benzoin in the presence of ammonium acetate as a nitrogen source of the pyrrole ring. Optical property of the tetraarylpyrroles obtained by the reaction was clarified by UV/Vis spectroscopy and/or time-dependent density functional theory (TD-DFT) calculations.

DOI： 10.3987/COM-17-13781

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

DOI： 10.1002/chin.201650044

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

A series of porphyrins fused with acenaphthylene, phenanthroline, and benzofluoranthene polycyclic aromatic rings were prepared by means of a 3+1 porphyrin synthesis approach and subsequent retro-Diels-Alder reaction of bicyclo[2.2.2]octadiene-fused precursors. Analysis of the magnetic circular dichroism spectra and the results of time-dependent DFT calculations are used to identify the reasons for the trends observed in the wavelengths and relative intensities of the Q bands of the products. Michl's perimeter model is used as a conceptual framework to explain the changes in the relative energies of the frontier -molecular orbitals.

DOI： 10.1002/chem.201602213

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In this study, hexagonal shape-persistent cyclophane with D-2h symmetry and rigid dihedral angles was obtained through the key SNAr reaction of perfluorobenzene moieties and dipyrroles. The X-ray analysis of the compound thus obtained revealed a hexagonal macrocyclic structure with D-2h symmetry due to the dihedral angles of 120 degrees and double 120 degrees for bicyclo[2.2.2]octadiene:fused dipyrrole and syn-diethanotetrahydroanthracene-fused dipyrrole, respectively. (C) 2016 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2016.07.086

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A complex of Cyclo[8]pyrrole with polyoxometalate, POM-to-Rings, was synthesized by anion exchange from cyclo[8]pyrrole sulfate. X-ray crystallographic study revealed the double-decker structure. (C) 2016 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2016.06.021

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

An acenaphthylene-fused cyclo[10]pyrrole 1b was selectively synthesized via an oxidative coupling reaction of the corresponding 2,2'-bipyrrole with the appropriate dianion template, croconate anion. The structure of 1b as the isolated largest cyclo[n]pyrrole was elucidated by X-ray crystallographic analysis. The absorption spectrum exhibited a markedly red-shifted, intensified L band at 1982 nm, which was interpreted by application of Michl's perimeter and Gouterman's 4-orbital models, supported by magnetic circular dichroism (MCD) data and theoretical calculations.

DOI： 10.1021/jacs.6b04941

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DOI： 10.1002/chin.201607059

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The synthesis of 1,2′-biazulenes was established by palladium-catalyzed homocoupling reactions of the corresponding 1-haloazulenes in the presence of ferrocene. The optical properties of the novel 1,2′-biazulenes were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behaviors of 1,2′-biazulenes were also examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV).

DOI： 10.1055/s-0035-1561418

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Language：Japanese   Publisher：The Surface Science Society of Japan  

DOI： 10.14886/sssj2008.36.0_289

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Preparation of 2- and 6-thienylazulene derivatives was established by the palladium-catalyzed direct cross-coupling reaction of 2- and 6-haloazulenes with the corresponding thiophene derivatives in good yield. Several thienylazulene derivatives were also used in the reaction with 2-chloroazulene derivatives in the presence of the palladium-catalyst to afford the thiophene derivatives with two azulene functions in good yield.

DOI： 10.1039/c5ob01317h

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Abstract

2‐ and 6‐arylazulene substrates (III) and (VIII) are prepared by cross‐coupling of aryl halides (I) with 2‐ or 6‐haloazulene (II) and (VII).

DOI： 10.1002/chin.201516092

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DOI： 10.1002/chin.201509071

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© 2015 Wiley-VCH Verlag GmbH &amp; Co. KGaA, Weinheim. Aryl-substituted 1,1,4,4-tetracyano-1,3-butadienes (FcTCBDs) and bis(1,1,4,4-tetracyanobutadiene)s (bis- FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro-electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis-FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi-electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions.

DOI： 10.1002/chem.201405004

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Language：English   Publishing type：Part of collection (book)   Publisher：Springer Japan  

Oligoporphyrins with a large fused π-electron system were successfully synthesized by the fusion of porphyrin chromophores with polycyclic aromatic hydrocarbons (PAHs). Oligoporphyrins fused with benzene units and zinc diporphyrins fused with PAHs were prepared and their electronic properties were examined. Electronic spectra showed strong absorption in the red to near-infrared (NIR) region. Not only the absorption maxima but also the number of absorption bands was affected by the fusion mode of the porphyrin chromophores. In the UV-vis spectra of the oligoporphyrins, three major absorption bands corresponding to Soret and Q bands were observed. A linearly fused trizinc triporphyrin with two benzene moieties showed strong Q-band absorption at 680nm, while split Q-band absorptions at 663 and 674nm were observed in the L-shaped triporphyrin. Preparation based on the retro-Diels-Alder reaction of the precursors with a bicyclo[2.2.2]octadiene skeleton did not give naphthacene- and pentacene-fused diporphyrins but instead gave naphthalene-, anthracene-, and chrysene-fused diporphyrins. In the chrysene-fused diporphyrin, the absorption maximum in the Q band was 624nm, which was similar to that of naphthalene-fused diporphyrin.

DOI： 10.1007/978-4-431-55357-1_2

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

4,8-Dihydropyrrol[3,4-f]isoindole was prepared from 4,7-dihydroisoindole based on the modified Barton-Zard reaction. Addition of phenylsulfenyl chloride followed by oxidation and dehydrochlorination gave phenylsulfonyldihydroisoindole, which underwent the smooth reaction with an isocyanoacetate under basic conditions to give 4,8-dihydropyrrol[3,4-f]isoindole-1,5- and 1,7-dicarboxylates in good yields. The pyrrolisoindole was successfully converted to the benzene-fused bisBODIPY, absorption maximum of which was 758 nm.

DOI： 10.3987/COM-14-S(K)91

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DOI： 10.1002/ejoc.201403556

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DOI： 10.1246/bcsj.20150165

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1,3-Bis(azulenylethynyl)azulene derivatives 9-14 have been prepared by palladium-catalyzed alkynylation of 1-ethynylazulene 8 with 1,3-diiodoazulene 1 or 1,3-diethynylazulene 2 with the corresponding haloazulenes 3-7 under Sonogashira-Hagihara conditions. Bis(alkynes) 9-14 reacted with tetracyanoethylene (TCNE) in a formal [2+2] cycloaddition-retroelectrocyclization reaction to afford the corresponding new bis(tetracyanobutadiene)s (bis(TCBDs)) 15-20 in excellent yields. The redox behavior of bis(TCBD)s 15-20 was examined by using CV and differential pulse voltammetry (DPV), which revealed their reversible multistage reduction properties under the electrochemical conditions. Moreover, a significant color change of alkynes 9-14 and TCBDs 15-20 was observed by visible spectroscopy under the electrochemical reduction conditions.

DOI： 10.1002/chem.201402939

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WORLD SCI PUBL CO INC  

A series of O-chelated BODIPYs fused with aromatic rings such as benzene and acenaphthylene at beta,beta-positions was synthesized as a near-infrared dye. The photophysical properties were examined by UV-vis-NIR absorption and fluorescence measurement. Acenaphthylene-fused O-BODIPYs showed a intense absorption at 750-840 nm with the epsilon of 10(5) M-1.cm(-1). and a fluorescene emission at 770-850 nm with the high Phi value of 0.06-0.43.

DOI： 10.1142/S1088424614500503

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The synthesis of 1‐methylthio‐ and 1,3‐bis(methylthio)azulenes with an electron‐donating group at the 6‐position as well as their transformation into the corresponding novel 1,1′‐bisazulene derivatives [cf.

DOI： 10.1002/chin.201425100

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Acetylene derivatives with azulenyl groups at both c‐atoms are prepared by palladium‐catalyzed alkynylation under Sonogashira—Hagihara conditions.

DOI： 10.1002/chin.201421099

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

1,3-Bisarylated-2,2'-biazulene 1 and 1,1'-bisarylated-2,2'-biazulene 1' were obtained by the Suzuki-Miyaura crosscoupling reaction of 1,1',3,3'-tetrahalo-2,2'-biazulene 2 with 4-tert-butylphenylboronic acid (3b). The other two halogen atoms were reductively removed by hydrogenation under the same reaction conditions. The major regioisomer 1 was obtained with a selectivity of up to 94% (15:1) and a combined yield of 1 and 1' of up to 77%.

DOI： 10.1246/cl.131142

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

Cyclo[8]pyrrole with eight 9,10-dihydroanthracene wings was synthesized by oxidative coupling of the corresponding 2,2'-bipyrrole in good yield. The molecular structure was determined by single crystal X-ray analysis. The three-dimensionally structured cyclo[8]pyrrole possessed a cavity created by a pair of slip-stacked cyclo[8]pyrroles.

DOI： 10.3987/COM-13-S(S)42

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The Hinsberg thiophene synthesis using 4,5,6,7-tetrahydro-4,7-ethanothiophene-5,6-dione and diethyl thiodiglycolate afforded a mixture of diethyl 4,8-dihydro-4,8-ethanobenzo[1,2-c;4,5-c']dithiophene-1,3-dicarboxylate and its dihydrate, although the yields were low. The latter dihydrate was converted to the former dithiophene in a good yield by the treatment with Ac2O and DMAP.

DOI： 10.3987/COM-13-S(S)53

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A series of O-chelated BODIPYs fused with aromatic rings such as benzene and acenaphthylene at β,β-positions was synthesized as a near-infrared dye. The photophysical properties were examined by UV-vis-NIR absorption and fluorescence measurement. Acenaphthylene-fused O-BODIPYs showed a intense absorption at 750–840 nm with the ε of 105 M-1.cm-1. and a fluorescence emission at 770–850 nm with the high Φ value of 0.06–0.43.<br />
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DOI： 10.1142/S1088424614500503

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© 2014 The Japan Institute of Heterocyclic Chemistry. Preparation of 2-aryl- and 6-heteroarylazulenes 2-6 and 8-10 was established by the palladium-catalyzed cross-coupling reaction of the corresponding haloazulenes with lithium aryl- and heteroarylmagnesium ate complexes, which were readily prepared from the corresponding aryl and heteroaryl halides. The reaction of 2-6 and 8-10, except for 3 and 8, with pyridine in the presence of Tf 2 O, followed by treatment with KOH in MeOH afforded the corresponding 2-aryl- and 6-heteroaryl-1,3-di(4-pyridyl)azulenes 11-16 in good yields.

DOI： 10.3987/COM-14-13102

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Synthesis of 2,2&#039;-diamino-1,1&#039;-biazulene derivatives 5 and 911 was established by copper-catalyzed homocoupling reaction of the corresponding 2-aminoazulenes 3 and 68. The palladium-catalyzed cross-coupling reactions of 6,6&#039;-dibromo- 1,1&#039;-biazulene derivative 9 were also established under the SuzukiMiyaura and SonogashiraHagihara conditions. © 2014 The Chemical Society of Japan.

DOI： 10.1246/cl.140333

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

Bicyclo[2.2.2]octadiene-fused (BCOD-fused) bis(benzoborondipyrromethene)s (bisbenzoBODIPYs) bearing electron-withdrawing groups such as fluorine and cyano groups were prepared either by incorporating tetrafluoroisoindole moieties into BODIPY chromophores or by introducing cyano or ethoxycarbonyl groups at the 3,5-positions. The BCOD-fused bisbenzoBODIPYs were quantitatively converted to the corresponding benzene-fused bisbenzoBODIPYs by a retro-Diels-Alder reaction. The pi-fused bisbenzoBODIPYs were found to have intense absorption in the near-infrared region and not to have any strong absorption bands in the visible region. Moreover, the bisbenzoBODIPYs were stable under atmospheric conditions.

DOI： 10.1039/c3ob41996g

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6-Methoxy- and 6-dimethylaminoazulenes with methylthio groups at the 1- or 1,3-positions have been prepared by electrophilic substitution of the corresponding azulenes with DMSO in the presence of acid anhydride, followed by treatment with Et 3 N. The products, 1-methylthioazulenes, reacted with Tf 2 O to afford the corresponding 1,1′-biazulene derivatives in moderate yields. The redox behavior of these azulene and 1,1′-biazulene derivatives was examined by cyclic voltammetry (CV), which revealed reversible electron transfers under electrochemical oxidation conditions. 6-Dimethylamino-1,3-bis(methylthio)azulenes with a heteroaiyl group at the 2-position were also prepared by the reaction of 6-dimethylamino-1,3- bis(methylthio)azulene with triflates of iV-containing heterocycles, i.e., pyridine, quinoline, isoquinoline, acridine, and 1,10-phenanthroline, followed by treatment with KOH in alcohols. © 2013 The Chemical Society of Japan.

DOI： 10.1246/bcsj.20130275

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Acetylene derivatives with an azulenyl group at both terminals have been prepared by palladium-catalyzed alkynylation under Sonogashira-Hagihara conditions. These alkynes reacted with tetracyanoethylene and 7,7,8,8-tetracyanoquinodimethane in a formal [2 + 2] cycloaddition-retroelectrocyclization reaction to afford the corresponding new tetracyanobutadienes (TCBDs) and dicyanoquinodimethanes (DCNQs), respectively, in excellent yields. Intramolecular CT absorption bands were found in the UV-vis spectra of the novel chromophores, and CV and DPV showed that they exhibited a reversible two-stage reduction wave, due to the electrochemical reduction of TCBD and DCNQ moieties. Color changes were also observed during the electrochemical reduction.

DOI： 10.1021/jo402104n

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Boron complexes of [14]triphyrins(2.1.1) were prepared from free-base [14]triphyrins(2.1.1) with phenylboron dichloride. The absorption spectrum of the meso-free β-alkyl-triphyrin boron complex in CH2Cl 2 showed a broad weak band at around 640 nm assigned to transition from B-phenyl to the triphyrin, while that of the meso-aryl benzotriphyrin boron complex showed only Soret and Q bands. © 2013 The Royal Society of Chemistry.

DOI： 10.1039/c3cc44788j

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

An acenaphthylene-fused cyclo[8]pyrrole was synthesized by using an oxidative coupling reaction of the corresponding 2,2-bipyrrole. Two conformational isomers 1a and 1b were isolated, and their molecular structures were elucidated by X-ray crystallographic studies. The less-polar and lower-symmetry 1b isomer can be converted into the 1a isomer through a thermal ring flip. Application of the perimeter model developed by Michl to magnetic circular dichroism spectroscopic data and theoretical calculations demonstrate that there is a marked redshift of the near-IR absorption maxima relative to cyclo[8]isoindole because there is a significant stabilization of the LUMO due to the differing effects of a fused ring expansion with acenaphthylene and benzene moieties on the frontier molecular orbitals.

DOI： 10.1002/chem.201301294

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We have synthesized 13,13′-(3,5-bis(trifluoromethyl)phenyl)-6, 6′-bipentacene from a soluble bispentacenequinone precursor. Bispentacene takes orthogonal conformation in the solid state and exhibits four reversible redox potentials. In addition, a tetracyanobipentacenequinodimethane was obtained for the first time from the pure bispentacenequinone. © The Royal Society of Chemistry 2013.

DOI： 10.1039/c3ra41914b

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

9,10-Phenanthrenequinone (9,10-PQ) is one of the most abundant quinones among diesel exhaust particulates. Recent data have suggested that quinones induce apoptosis in immune, epithelial and tumor cells, leading to respirator illness; however, the mechanisms by which quinones induce apoptosis and the structure required for this remain unknown. We studied the antitumor activity of 9,10-PQ analogs against two human tumor cell lines, HCT-116 colon tumor cells and HL-60 promyelocytic leukemia cells. The loss of the cis-orthoquinone unit in 9,10-PQ abrogated its ability to induce apoptosis in the two tumor cell lines, and the LC50 values of these analogs were indicated over 10 mu M. An analog of 9,10-PQ in which the biaryl unit had been deleted displayed a reduced ability to induce tumor cell apoptosis, while the analogs 1,10-phenanthroline-5,6-dione (9) and pyrene-4,5-dione (10), which also had modified biaryl units, exhibited increased tumor cell apoptotic activity. The cis-orthoquinone unit in 9,10-PQ was identified as essential for its ability to induce apoptosis in tumor cells, and its biaryl unit is also considered to influence orthoquinone-mediated apoptotic activity. (C) 2013 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.bmcl.2013.06.015

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

A semiferrocene complex with a [14]triphyrin(2.1.1) (TriP) ligand has been synthesized. The structure and properties are characterized by X-ray crystallographic analysis, UV/Vis spectroscopy, and variable-temperature 1 H NMR spectroscopy. The Fe II and Fe III complexes are electrochemically reversible. Copyright © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

DOI： 10.1002/anie.201302815

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

The non-luminous precursor, 2-(1-pyrenyl)-9,10-dihydro-9,10- ethanoanthracene-11,12-dione, was photochemically converted to highly-fluorescent 2-(1-pyrenyl)anthracene quantitatively in solution and in the PMMA film and the fluorescence quantum yield of the acene in benzonitrile was as high as 0.99. © The Royal Society of Chemistry 2013.

DOI： 10.1039/c3cc40827b

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1-, 2-, and 6-(Ferrocenylethynyl)azulene derivatives 10-16 have been prepared by palladium-catalyzed alkynylation of ethynylferrocene with the corresponding haloazulenes under Sonogashira-Hagihara conditions. Compounds 10-16 reacted with tetracyanoethylene (TCNE) in a [2+2] cycloaddition-cycloreversion reaction to afford the corresponding 2-azulenyl-1,1,4,4,-tetracyano-3-ferrocenyl-1,3-butadiene chromophores 17-23 in excellent yields. The redox behavior of the novel azulene chromophores 17-23 was examined by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.

DOI： 10.1002/chem.201202257

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Highly fluorescent naphthacene derivatives and their photoconvertible precursors were synthesized for irreversibly photo-responsive fluorescent molecules. The fluorescence quantum yields (Φf) of the precursors were less than 0.02, and the precursors can be converted to the highly fluorescent naphthacene derivatives (Φf = 0.67-0.70) quantitatively by photo-irradiation. © 2013 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2013.01.014

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

Metalation of 6,13,20,21-tetrakis(4-methyl-phenyl)-22H-tribenzo[14]triphyrin(2.1.1) with PtCl2 gave a platinum(II) complex having a square-planar coordination structure with two pyrrolic nitrogen atoms and two chloride ions, with a saddle-shaped macrocycle. This platinum(II) complex was easily oxidized by air to an octahedral platinum(IV) complex coordinated by three pyrrolic nitrogen atoms as a tridentate monoanionic cyclic ligand and three chloride ions. When platinum(II) triphyrin was crystallized in air, an oxygen atom was incorporated between two alpha-carbon atoms of the pyrroles as an oxygen bridge to intercept the 14 pi aromatic system.

DOI： 10.1021/ic302624h

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P-n junction solar cells based on anthradithiophene (ADT) as a p-type semiconductor were fabricated by using the photoprecursor method in which an alpha-diketone-type precursor was spin-coated and then transformed to ADT in situ by photoirradiation. Combination with PC71BM as an n-layer material led to 1.54% photoconversion efficiency.

DOI： 10.1039/c3cc46178e

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Ene-diyne systems possessing 1- and 2-azulenyl groups at the periphery were prepared by palladium-catalyzed cross-coupling reaction of 1- and 2-ethynylazulenes with 9-dibromomethylene-9H-fluorene and 9,10- bis(dibromomethylene)-9,10-dihydroanthracene or 2-iodoazulene with 9,10-bis(diethynylmethylene)-9,10-dihydroanthracene under Sonogashira-Hagihara conditions. The redox behavior of the ene-diyne compounds was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Moreover, a significant color change of the ene-diyne derivatives was observed with visible spectroscopy under electrochemical reduction conditions. Copyright © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

DOI： 10.1002/ejoc.201201397

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Ethyl 12-oxo-4,11-dihydro-4,11-ethanonaphth[2,3-f]isoindole-1-carboxylate (2) was prepared from 7-tert-butoxynorbornadiene and quantitatively converted to ethyl naphth[2,3-f]isoindole-1-carboxylate (3) by the thermal or photochemical cheletropic reaction. Ethyl naphth[2,3-f] isoindole-1-carboxylate (3) existed in a 2H-form both in solution and as a solid, and gradually dimerized to give a dianthradiazafulvalene derivative under aerobic conditions.

DOI： 10.1039/c2ra22870j

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：World Scientific Publishing Co. Pte Ltd  

Magnetic circular dichroism (MCD) spectroscopy and TD-DFT calculations are used to analyze the electronic structure and optical properties of low-symmetry acenaphthoporphyrins with AAAB, ABAB and AABB structures. Evidence for dual fluorescence caused by tautomerism has been identified in the emission spectra of the AAAB and ABAB compounds. The sign sequences observed for the Q and B bands in the MCD spectra have been used to validate the results of the TD-DFT calculations. An anomalous +/- sign sequence is observed in the B band region with ascending energy similar to that reported previously for metal tetraphenyltetraacenaphthoporphyrin complexes. Copyright © 2013 World Scientific Publishing Company.

DOI： 10.1142/S1088424613500727

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1-Ethynylazulenes connected by several arylamine cores reacted with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2+2] cycloaddition-cycloreversion reaction to afford the corresponding tetracyanobutadiene (TCBD) and dicyanoquinodimethane (DCNQ) chromophores, respectively, in excellent yields. The intramolecular charge-transfer (ICT) characters between the donor (azulene and arylamine cores) and acceptor (TCBD and DCNQ units) moieties were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the new TCBD and DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions. 1-Ethynylazulenes connected by several types of arylamine cores reacted with TCNE and TCNQ in formal [2+2] cycloadditions to afford corresponding tetracyanobutadiene and dicyanoquinodimethane chromophores, respectively. Cyclic voltammetry of the chromophores revealed their multistep reduction properties; significant color changes were also visible during electrochemical reduction. Copyright © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

DOI： 10.1002/ejoc.201301006

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Elusive in its free-base form, the core-modified contracted porphyrin thiatriphyrin(2.1.1) was prepared with p-tolyl substituents by intramolecular McMurry coupling and then converted into various alkoxy-substituted analogues (see scheme; DBU=1,8-diazabicyclo[5.4.0]undec-7-ene). In the presence of trifluoroacetic acid (TFA), each of these compounds was transformed into the protonated thiatriphyrin(2.1.1), which exhibited moderate aromaticity. © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

DOI： 10.1002/anie.201209678

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The synthesis of 1,6′-biazulenes 3a and 3b and 1,6′:3,6″- terazulenes 7a and 7b was established by one-pot reactions via the Zincke-type ring-opening of the corresponding pyridinium salts with diethylamine, followed by the reaction with cyclopentadiene in the presence of sodium methoxide. The intramolecular charge-transfer characters between azulene rings were investigated by UVvis spectroscopy and theoretical calculations. © 2013 The Chemical Society of Japan.

DOI： 10.1246/cl.130157

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Bis(azulenylethynyl)thiophenes, terthiophenes, and dithienothiophenes have been synthesized by the Pd-catalyzed cross-coupling of the corresponding diiodothiophenes with 1- and 6-ethynylazulenes under Sonogashira-Hagihara conditions.

DOI： 10.3987/COM-12-S(N)63

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Ethanonaphthoporphyrins with a halogen atom at the zeta position were prepared by the [3+1] porphyrin synthesis of halogen-substituted ethanobenz[f]isoindole with a tripyrrane derivative. The halogeno porphyrins were converted to the corresponding ethynyl and pinacolatoboronyl compounds by Sonogashira and borylation reactions, respectively. Suzuki, Sonogashira, and Glaser coupling reactions of these ethanonaphthoporphyrins gave bis-porphyrins connected with no atom, acetylene, and butadiyne, respectively. Retro Diels-Alder reaction of these bis-porphyrins brought about the conversion of bicyclo[2.2.2]octadiene (BCOD) to benzene moieties to give bis-naphthoporphyrins, quantitatively.

DOI： 10.3987/COM-12-S(N)50

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Azulene-substituted butadiynes have been prepared by Cu-mediated cross- and homo-coupling reactions. The azulene-substituted butadiynes reacted with tetracyanoethylene in a formal [2 + 2] cycloaddition reaction to afford the corresponding 1,1,4,4-tetracyanobutadiene chromophores, in excellent yields. Further [2 + 2] cycloaddition with TTF and TCNE gave novel donor-acceptor chromophores and novel azulene-substituted 6,6-dicyanofulvene derivatives.

DOI： 10.1039/c2ob26028j

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

Bicyclo[2.2.2]octadiene (BCOD) fused azuliporphyrins were synthesized by 3+1 porphyrin synthesis of azulitripyrranes with diformylpyrroles. Subsequent retro-Diels-Alder reaction of the BCOD-fused azuliporphyrins afforded azulibenzo, azulidibenzo-, and azulitribenzoporphyrins 1-5. NMR and UV/Vis spectra, as well as nucleus-independent chemical shift (NICS) calculations revealed that 1-5 and their diprotonated dications exhibit relatively low porphyrinoid aromaticity, which was dependent on the position and number of fused benzene rings present.

DOI： 10.1002/chem.201201399

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Language：English   Publishing type：Part of collection (book)   Publisher：Wiley-VCH  

DOI： 10.1002/9783527652532.ch11

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

Bisdimethylfluorenylamino-based push-pull dyes bearing one or two benzo[c]thiophene and its precursor bicyclo[2.2.2]octadiene (BCOD) fused thiophene as it bridge have been synthesized. The effect of fused-ring on thiophene bridge for the spectroscopic and electrochemical properties of these dyes has been investigated. Dye-sensitized solar cells fabricated with these dyes show moderate photovoltaic properties. (C) 2012 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2012.04.052

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

Abstract

For the first time, an efficient synthesis of 2‐heteroarylazulene derivatives through electrophilic substitution without using a transition‐metal catalyst is established.

DOI： 10.1002/chin.201222136

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

Arylethynyl-2H-cyclohepta[b]furan-2-ones reacted with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2 + 2] cycloaddition reaction, followed by ring opening of the initially formed cyclobutene derivatives, to afford the corresponding dicyanoquinodimethane (DCNQ) chromophores in excellent yields. The intramolecular charge-transfer (ICT) interactions between the 2H-cyclohepta[b]furan-2-one ring and DCNQ acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties depended on the number of DCNQ units in the molecule. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.

DOI： 10.1039/c2ob06931h

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

6,13-Diiododibenzo[a,h]anthracene and 5,8-diiodopicene were synthesized by AuCl-catalyzed double cyclization. The highly selective reaction yielded a new class of pen-halogenated fused aromatics. (C) 2012 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2012.01.071

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

5,14-alpha-Diketopentacene, a structural isomer of 6,13-alpha-diketopentacene, was prepared from pentacene in three steps. In addition to the typical n-pi* absorption of the diketone moiety at around 468 nm and the anthracene-like absorption at 333, 349, and 367 nm, a broad absorption was observed at around 386 nm, which could be assigned to an intramolecular charge-transfer absorption from anthracene to the diketone moiety. 5,14-alpha-Diketopentacene could be converted into pentacene quantitatively by photoirradiation at 405 and 468 nm in toluene with quantum yields of 2.3 and 2.4%, respectively, and these values are higher than the quantum yield of 1.4% obtained for 6,13-alpha-diketopentacene irradiated at 468 nm. The quantum yields in acetonitrile were lowered to 0.33 and 0.28% with irradiation at 405 and 468 nm. The crystal structure of 5,14-alpha-diketopentacene showed a CH-pi interaction and pi-pi stacking between neighbouring anthracene and benzene moieties. The lower solubility of 5,14-alpha-diketopentacene compared with the 6,13-isomer could be explained by this crystal structure.

DOI： 10.1002/ejoc.201101736

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An efficient synthesis of 2-heteroarylazulene derivatives was established via electrophilic substitution. The reaction of 6-dimethylamino-1,3- di(methylthio)azulene (1a) with the triflate of N-containing heteroarenes proceeded in the presence of excess heteroarenes to afford the corresponding 2-dihydroheteroarylazulene derivatives 3-7. The 2-dihydroheteroarylazulene derivatives were readily converted into the desired 2-heteroarylazulene derivatives 8-11 by the treatment with KOH in alcohols in excellent yields, except for 4 and 5. © 2012 The Japan Institute of Heterocyclic Chemistry.

DOI： 10.3987/COM-11-12373

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

Benzene-fused bis-(borondipyrromethene)s (bis-BODIPYs) were synthesized by retro-Diels-Alder reaction of the corresponding bicyclo[2.2.2]octadiene-fused (BCOD-fused) bis-BODIPYs, which were, in turn, prepared from 4,8-ethano-4,8-dihydropyrrolo[3,4-f]isoindole derivatives. The pi-fused bis-BODIPY chromophores were designed to show intensive absorption and strong fluorescence in the near-infrared region and not to have any strong absorption in the visible region. A 6,10-dibora-5a,6a,9a,10a-tetraaza-s-indaceno[2,3-b:6,5-b']difluorene derivative (syn-bis-benzoBODIPY) obtained by a thermal retro-Diels-Alder reaction of the corresponding BCOD-fused BODIPY dimer has strong absorption and emission bands at 775 and 781 nm, respectively. The absolute quantum yield is 0.36. The absorption is more than 5.0 times stronger than other absorptions observed in the visible region. In the case of 6,15-dibora-5a,6a,14a,15a-tetraaza-s-indaceno[2,3-b:6,7-b']difluorene derivatives (anti-bis-benzoBODIPY), the absorption and emission maxima exceed 840 nm.

DOI： 10.1039/c2ob25930c

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

Hole mobility was evaluated by top-contact bottom gate field effect transistor and time resolved microwave conductivity measurements in 2,6-dithienylanthracene and hexyl-substituted 2,6-dithienylanthracene films prepared by spin-coating of their alpha-diketone precursors followed by photoirradiation, revealing enough high potentials for semiconducting films with charge carrier mobilities of 0.8-0.9 cm(2) V-1 s(-1) in the photo-irradiated films.

DOI： 10.1039/c2cc35439j

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WORLD SCI PUBL CO INC  

A series of benzoporphycenes and naphthoporphycenes and their zinc complexes were prepared from bicyclo[2.2.2]octadiene fused porphycenes by a retro-Diels-Alder reaction and their photophysical properties were studied. Free-base tetranaphthoporphycene was not soluble in common organic solvents, but zinc tetranaphthoporphycene was slightly soluble in pyridine and showed B- and Q-bands at 507 and 690 nm, respectively. Dinaphthoporphycene showed broad B- and Q-bands due to its lower symmetry. Tetrabenzo-, dibenzo-, and dinaphthoporphycenes showed fluorescence at 673, 654, and 670 nm with quantum yields of 0.32, 0.42, and 0.31, respectively, although their precursors were non-fluorescent. Zinc complexes of tetrabenzo-, dibenzo-, tetranaphtho-, dinaphthoporphycenes and their bicyclo[2.2.2]octadiene-fused precursors revealed moderate fluorescence with quantum yields of 0.15-0.37. The crystal structures of tetrabenzo-and dibenzoporphycenes showed herringbone structures, while the zinc tetrabenzoporphycene showed a hexagonal box-structure with six pyridine ligands inside.

DOI： 10.1142/S1088424611003823

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WORLD SCI PUBL CO INC  

Facing zinc bisporphyrins connected with diethanoanthracene and diethanonaphthacene (syn-1 and syn-2) are prepared by double [3+1] porphyrin synthesis of tripyrranedicarbaldehyde with syn-5,11-dimethoxy-4,6,10,12-tetrahydro-4,12;6,10-diethanoanthracene[2,3-c;7,8-c']dipyrrole and syn-4,7,11,14-tetrahydro-4,14;7,11-diethanonaphthacene[2,3-c;8,9-c']dipyrrole. These bisporphyrins contain large clefts with different sizes capable for complexation with fullerenes such as C-60 and C-70. These designed syn-oriented bisporphyrins serve as effective and selective molecular tweezers for C-70. Binding affinity of the zinc bisporphyrins, namely, syn-1 and syn-2, towards C-60 and C-70 in solution is determined by employing UV-vis spectrophotometric technique. Values of binding constants (K) in toluene for the non-covalent complexes of syn-1 with C-60 and C-70 are estimated to be 3.1(4) x 10(4) and 5.0(2) x 10(5) M-1, respectively, and those of syn-2 with C-60 and C-70 are enumerated to be 2.1(4) x 10(4) and 1.70(13) x 10(5) M-1, respectively. Binding of C-60 and C-70 in the clefts of syn-1 and syn-2 is clearly demonstrated by the crystal structures of C-60/syn-1, C-70/syn-1, C-60/syn-2, and C-70/syn-2 complexes. In the crystal structures with C-70, the directions of the long axis of C-70 are found to be quite different: in the case of C-70/syn-1 complex the axis lies perpendicularly to the line connecting two zinc atoms; however, for the C-70/syn-2 complex, the axis occupies in-plane to the same line. Both the clefts of syn-1 and syn-2 are induced to fit the included fullerenes by domed out-of-plane distortion of porphyrin rings. Moreover, the bicyclo[2.2.2]octadiene moieties of syn-1 are widened by complexation with the fullerenes, while the same moieties of syn-2 are narrowed by the complexation. Therefore, syn-1 catches the fullerenes at the shallow part of the cleft. On the other hand, syn-2 catches the fullerenes at the bottom part of the cleft. NMR experiments of the complexes in THF-d(8) also support these orientations even in solution.

DOI： 10.1142/S1088424611003872

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Bicyclo[2.2.2]octadiene(BCOD)-fused diazaporphyrin was synthesized by the reaction of BCOD-fused dipyrromethane with sodium nitrite in acetic acid/ethanol in the presence of copper(II) acetylacetonate. This soluble precursor was converted into the semiconducting thin film of (tetrabenzodiazaporphyrinato) copper(II) by heating after fabrication via spin-coating. © 2011 World Scientific Publishing Company.

DOI： 10.1142/S1088424611003641

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

This paper focuses on the synthesis of new aromatic compounds by thermal, photochemical, or oxidative cleavage reaction of the corresponding precursors. The precursor-methods are useful for the derivatization of the non-soluble aromatic compounds. We have applied retro Diels-Alder reactions for the preparation of new pi-expanded porphyrinoid compounds such as [14] tribenzo-triphyrin (2.1.1), tetrabenzoporphycene, dodecasubstituted porphycene, tetraanthraporphyin, butadiyne-linked tetrabenzoporphyrin dimer, and so on. We have investigated the photocleavage synthesis of pentacenes from the corresponding alpha-diketone precursors. This photoreaction enabled us to prepare 1,4,8,11-tetrasubstituted pentacene. The synthesis of new pentacene derivatives with electron-withdrawing substituents at 6,13-positions by oxidative cleavage reaction will be also reported.

DOI： 10.5059/yukigoseikyokaishi.69.802

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Retro: Cyclo[8]isoindole, which has a saddle-shaped geometry (see picture, 2), was synthesized by oxidative coupling of a bicyclo[2.2.2]octadiene(BCOD)- fused 2,2′-bipyrrole followed by a retro-Diels-Alder reaction of BCOD-fused cyclo[8] pyrrole (1). Key trends in the optical spectra of ring-annelated cyclo[8]pyrroles are identified based on magnetic circular dichroism spectra and theorectical calculations. Copyright © 2011 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

DOI： 10.1002/anie.201007510

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

A pi-expanded BODIPY dye with an intramolecular boronate skeleton was synthesized by retro Diets-Alder reaction of the bicyclo[2.2.2]octadiene (BCOD)-fused BODIPY and the subsequent O-chelation. The photophysical and electrochemical properties were examined by UV-vis, fluorescence, CV measurements, and DFT calculation. This BODIPY exhibited the absorption and emission over a visible-NIR region at 600-850 nm. O-chelated BODIPY showed a bathocromic shift compared to F-BODIPYs. This dye showed a bright fluorescence emission at 733 nm with the high phi value of 0.58. (C) 2011 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2011.03.016

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

DOI： 10.1002/chem.201003628

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

We have investigated the role of fused benzo rings on the electronic structures and intramolecular energy relaxation dynamics in a series of benzoporphyrins (Bpl, syn-Bp2, anti-Bp2, Bp3, and Bp4) by using time-resolved fluorescence measurements and theoretical calculations. Interestingly, even though anti- and syn-Bp2 have the same number of fused anti-Bp2 benzo rings, in the respective absorption spectra, shows an obvious splitting of B(x) (Q(x)) and B(y) (Q(y)) states, whereas syn-Bp2 exhibits degenerate B and Q bands. These features provide two dynamical models for the effect of the position of substituted benzo rings on the intramolecular energy relaxation dynamics. syn-Bp2 gives rise to similar intrarnolecular dynamics from the B state to the Q state in the case of ZnTPP having Do molecular symmetry. On the other hand, anti-Bp2 shows split B and Q bands in the order B(y) &gt; B(x) &gt; Q(x) &gt; Q(y), which leads a superimposition of the Q(x) (0,0) and Q(y) (1,0) bands. This overlap generates a strong coupling between these two states, which results in a direct internal conversion from B(x) (0,0) to Q(y) (0,0). This observation suggests that the anti-type fused position of benzo rings leads to a new mechanism in internal conversion from the B to the Q state. On the basis of this work, further insight was obtained into the effect of fused benzo rings on the photophysical properties of benzoporphyrins, providing a detailed understanding of the structure-property relationship in a series of benzoporphyrins.

DOI： 10.1021/jp200493p

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

The synthesis of dodecasubstituted porphycenes has not been reported, to date. Herein, the preparation of tetramethyloctaethylporphycene by a McMurry-type coupling of 3,3', 4,4'-tetraethyl-5,5'-diformyl-2,2'-bipyrrole was attempted at first, but dodecasubstituted porphycene was not successfully obtained and only pyrrolocyclophene was obtained. The structure of the pyrrolocyclophene was determined by H-1 NMR spectroscopy, FAB MS, and X-ray crystal-structure analysis. The pyrrolocyclophene was not successfully oxidized to porphycene. Then, the McMurry-type coupling of bicyclo[2.2.2]octadiene (BCOD)-fused 5,5'diacyl-2,2'-bipyrroles was performed and tetra-meso-octa-beta-substituted (dodecasubstituted) porphycenes were successfully obtained for the first time. The structures were determined by H-1 NMR spectroscopy and X-ray crystal-structure analysis. The crystal structures and NMR spectra were compared carefully with octasubstituted porphycenes, and there was a good correlation between the position of the substituents, the N1-N2 and N1-N4 distances of the porphycene inner nitrogen atoms, and NMR chemical shifts of the inner NH protons, which expressed the strength of N-H center dot center dot center dot N hydrogen bonding between N1 and N2. These results suggested that the BCOD structure was relatively compact compared with common alkyl groups and that was why the dodecasubstituted porphycenes were available this time. UV/Vis absorption and fluorescence properties are also discussed.

DOI： 10.1002/chem.201002788

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

5,12-Dicyanonaphthacene and 6,13-dicyanopentacene have been synthesized for the first time. The LUMO and HOMO levels are deepened as predicted and fabricated organic field-effect transistors (OFETs) showed ambipolar responses with carrier mobilities of 10(-3) cm(2)/V.s.

DOI： 10.1021/ol200145r

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The ene-diyne systems 1 and 2, possessing ferrocenyl groups at the periphery, were prepared by a simple one-pot Sonogashira-Hagihara coupling reaction of ethynylferrocene with 9-dibromomethylene-9H-fluorene (4) and 9,10-bis(dibromomethylene)-9,10-dihydroanthracene (5). Ene-diyne 1 reacted with tetracyanoethylene (TCNE) in a formal [2+2] cycloaddition reaction, followed by ring opening of the initially formed [2+2] cycloadduct, cyclobutene, to afford the corresponding 1,1,4,4-tetracyanobutadiene (TCBD) derivative 6 in good yield. The redox behavior of the ene-diyne compounds 1 and 2, and the TCBD derivative 6 was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their electrochemical oxidation properties with multi-electron transfer depending on the number of ferrocene units in the molecule, in addition to the two-electron reduction of the TCBD moiety in the case of TCBD derivative 6. Moreover, a significant color change was observed by visible spectroscopy under electrochemical oxidation conditions and under reduction conditions in the case of TCBD derivative 6. Ene-diyne systems with ferrocenyl groups at the periphery were prepared by theSonogashira-Hagihara reaction and reacted with tetracyanoethylene in a [2+2] cycloaddition reaction to afford the 1,1,4,4-tetracyanobutadiene derivative in goodyield. The redox behavior was examined by cyclic voltammetry and differential pulse voltammetry; significant color changes were observed. Copyright © 2011 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

DOI： 10.1002/ejoc.201100650

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Novel bis(3-methylthio-1-azulenyl)methyl cations 3a + and 3b + and dications 4a 2+ and 4b 2+ were synthesized by thehydride abstraction reaction of the corresponding hydride derivatives 7a, 7b, 8a, and 8b, which were readily prepared by the acid-catalyzed condensation reaction of 6a and 6b with the corresponding aldehyde and dialdehyde with DDQ. The pK R + values of novel cations 3a + and 3b + and dications 4a 2+ and 4b 2+ were determined spectrophotometrically to examine the thermodynamic stability of these carbocations. The redox behavior of the mono- and dications was also examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their reversible electrochemical reduction properties, except for the case of dication 4b 2+ . Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions. Dications 4a 2+ and 4b 2+ were also chemically reduced by Zn powder to afford thienoquinoid compounds 9a and 9b, respectively. Bis(3-methylthio-1-azulenyl)methyl cations and dications were synthesized from the corresponding hydride derivatives, which were prepared by the acid-catalyzed condensation reaction of 1-methylthioazulenes with aldehydes and dialdehydes with DDQ. These novel carbocations exhibited reversible electrochemical reduction properties. © 2011 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

DOI： 10.1002/ejoc.201001212

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

Novel bisimide-fused acenes were synthesized via bismuth triflate mediated double-cyclization reaction of acid chlorides and isocyanates. Their optical and electrical properties revealed significantly smaller HOMO-LUMO gaps compared with those of their parent acenes. Fabricated OFET based on tetracene bisimide showed n-type OFET outputs.

DOI： 10.1039/c1cc13980k

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

The metal-free and meso-free [14]triphyrin(2.1.1) compound was successfully prepared based on the intramolecular McMurry coupling reaction of diformyl-tripyrrane in 16% yield, and was converted to the bowl-shaped Mn(I)(TriP)(CO)(3) and Re(I)(TriP)(CO)(3).

DOI： 10.1039/c0cc04286b

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

Free base and zinc porphyrins are linked with fullerene (C(60)) through beta,beta`-pyrrolic positions rather than meso-positions by Diels-Alder reaction of monoanthraporphyrins (H(2)P-mA and ZnP-mA) and C(60) to afford a pi-expanded free base porphyrin-fullerene dyad (H(2)P-C(60)) and its zinc porphyrin-fullerene dyad (ZnP-C(60)) in 86 and 51% yield, respectively The X-ray crystallographic analysis of ZnP-C(60) showed two comma-shaped swirls-like structure in a unit cell The intramolecular center-to-center and edge-to-edge distances between the porphyrin and fullerene moieties were 11 5 and 2 5 angstrom, respectively The porphyrins and fullerenes were packed in layer-by-layer structure and the porphyrins lied down in parallel The Intermolecular center-to-center distances between the neighboring fullerenes were 10 252, 10028, and 10 129 angstrom, which were less than typical van der Waals distance and the pi-pi interaction spread two-dimensionally The energy of the charge-separated (CS) state of ZnP-C(60) (1 11 eV) determined by differential-pulse voltammetry measurements in benzonitrile is significantly lower than those of zinc porphyrin-C(60) dyads linked at meso positions because of the low oxidation potential of the a-expanded ZnP moiety The CS energy of ZnP-C(60) in a nonpolar solvent such as toluene (1 40 V) is lower than the triplet excited state of C(60) ((3)C(60)*), enabling us to attain a longed lived triplet CS state (8 1 mu s) in toluene, detected by nanosecond laser flash photolysis experiments The distance between unpaired electrons in the triplet CS state was determined by the EPR spectrum to be 9 1 angstrom, which agreed with the distance between a zinc atom of the porphyrin and a carbon edge of C(60) in the crystal structure of ZnP-C(60) The rate constants of photoinduced electron transfer and back electron transfer of H(2)P-C(60) and ZnP-C(60), which were determined by femtosecond and nanosecond laser flash photolysis measurements, were analyzed in light of the Marcus theory of electron transfer

DOI： 10.1021/jp102966x

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

15-Acetoxy- and 15-hydroxy-6,13-dihydro-6,13-ethanopentacenes sublimed over 300 degrees C and no pentacene was formed below the temperature. The precursors bearing chlorinated epithiomethano bridges suffered complicated decomposition to give oligomeric pentacene derivatives. The precursor bearing an epithio-oxomethano bridge underwent smooth and clean conversion to pentacene by heat or light. An organic field-effect transistor fabricated by the spin-coating method of the precursor followed by light irradiation at 120 degrees C showed a good FET performance of mu=2.5 x 10(-2) cm(2) V-1 s(-1) and on/off ratio=3.8 x 10(4). (C) 2010 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2010.06.051

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

Bicyclo[2.2.2]octadiene(BCOD)-fused trithiasapphyrin was prepared by 3+2 condensation of BCOD-fused thiatripyrrane with BCOD-fused bithiophene. The BCOD-fused trithiasapphyrin was successfully converted to pentabenzo[b,g,l,q,v]sapphyrin by the thermal retro-Diels-Alder reaction. In this case, trithiapentabenzo[b,g,l,q,v]- and trithiadibenzo[g,q]sapphyrins were selectively prepared by control of the temperature in the thermal retro-Diels-Alder reaction. (C) 2010 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2010.06.086

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

A series of pi-expanded boron-dipyrromethenes (BODIPYs) fused with aromatic rings at beta,beta-positions, such as benzene, acenaphthylene, and benzofluoranthene were prepared by the reaction of BF(3)center dot OEt(2) with bicyclo[2.2.2]octadiene-fused dipyrromethene and the subsequent retro Diels-Alder reaction. These BODIPYs exhibited the absorptions and the fluorescence emissions over wide range of visible-near infrared region at 500-800 nm. BODIPYs composed of two fluorantho[8,9-f]isoindoles absorbed and emitted at red-region over 750 nm with absolute fluorescence quantum yield (Phi(f)) of ca. 0.3, although they are unstable under air in room light. BODIPY composed fluorantho[8,9-f]isoindole and acenaphtho [1,2-c]pyrrole was stable and showed a bright fluorescence emission at 695 nm with high Phi(f) of 0.70. (C) 2010 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2010.06.045

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Tetrabenzoporphyrins fused with fluoranthenes were prepared by the retro Diels-Alder reaction of the precursors composed of a porphyrin and four fluoranthenes connected with bicyclo[2.2.2]octadiene (BCOD). These porphyrins exhibited the Soret (480-494 nm, epsilon = 243,000-277,000) and intense Q bands (739-760 nm, epsilon = 375,000-509,000). Free bases and Zn complexes of them fluoresce at 760 nm and 746 nm with small Storks shifts and high quantum yields of 30 and 10 %, respectively.

DOI： 10.3987/COM-09-S(S)98

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The syntheses of 1,4,8,11-tetraphenylpentacene and 1,4,8,11-tetra(2'-thienyl)pentacene are described via photodecarbonylation of the corresponding alpha-diketone precursors. (C) 2010 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2010.01.009

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

4,11-Ethano-4,11-dihydro-2H-anthra[2,3-c]pyrrole and 4,11-ethano-4,11-dihydroanthra[2,3-c]thiophene derivatives were prepared from the corresponding bicyclo[2.2.2]octadiene-fused five-membered heterocycles by the Diels-Alder reaction with in situ generated alpha, alpha&apos;-dibromo-o-xylylene derivatives. Their thermogravimetric analyses showed evapolation without formation of 2H-anthra[2,3-c]pyrrole and anthra[2,3-c]thiophene derivatives under the atmospheric pressure.

DOI： 10.3987/COM-09-S(S)102

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：TAYLOR & FRANCIS LTD  

This article describes the preparation of (ethylenedithio)bicyclo[2.2.2]octadiene-fused porphyrins 13 and 14a,b as soluble precursors of 2,3-dihydrobenzo[1,4]dithiin-fused porphyrins and the retro Diels-Alder conversion of the precursors 13 and 14a,b.

DOI： 10.1080/10426501003773449

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

Tetrameric porphyrin formation of 2-hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene-fused porphyrin pentamers. Thermal conversion of the pentamers gave fully pi-conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully pi-conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD-DFT calculations, the HOMO level is 0.49 eV higher than the HOMO-1 level. The LUMO and LUMO + 1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single-electron transitions (683 nm: 86%, HOMO -&gt; LUMO; 680 nm: 86%, HOMO -&gt; LUMO + 1). The two-photon absorption (TPA) cross section value (sigma((2))) of the benzene-fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional pi-conjugation pathways.

DOI： 10.1002/chem.200903196

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

A new alpha-diketoporphyrin and the corresponding Pd complex were prepared from the monoanthroporphyins and their photochemical properties were investigated by measurements of absorption and emission spectra, fluorescence lifetimes, laser flash photolysis, cyclic voltammetry, and theoretical calculations. Intramolecular electron transfer from the porphyrin singlet excited state to the diketone moiety was observed for the free base alpha-diketoporphyrin in benzonitrile, but this was not observed in toluene. Photoreactivity of the alpha-diketoporphyrins was also examined by irradiation at the Soret and Q bands. When the Soret band of the freebase alpha-diketoporphyrin was irradiated, cleavage of the diketone moiety occurred to afford the monoanthroporphyrin with the release of two CO molecules quantitatively in both benzonitrile and toluene. When the Q band of the freebase alpha-diketoporphyrin was irradiated, no photocleavage reaction occurred in toluene. In contrast to the freebase alpha-diketoporphyrin, the photocleavage reaction of the Pd complex occurred with irradiation at the Q band as well as the Soret band to afford the monoanthroporphyrin quantitatively in toluene. The photocleavage reaction proceeded much more effectively in toluene than in benzonitrile. The occurrence of rapid photoinduced electron transfer from the singlet excited state porphyrin to the diketone moiety, which was detected by femtosecond laser flash photolysis measurements, results in a significant decrease in the singlet excited state lifetime, prohibiting the photocleavage reaction in benzonitrile. Thus, the Pd alpha-diketoporphyrin can act as an excellent precursor for the corresponding acene in toluene. The photocleavage process provides a convenient and inexpensive method to make the thin film.

DOI： 10.1039/b923220f

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

Enediyne scaffolds connected by a 9,10-anthracenediyl spacer as a redox-active substructure with 6-azulenyl groups as pi-electron-accepting groups in their periphery (3a and 3b) have been prepared by a one-pot reaction involving repeated Pd-catalyzed alkynylation of 6-haloazulenes 7b and 7c with bis(enediyne) derivative 6. The azulene-substituted bis(enediyne)s 3a and 3b exhibited two reversible one-step, two-electron reduction proper-ties upon cyclic voltammetry (CV) attributable to the formation of dianionic and tetraanionic species. The electrochemical reduction of 3a and 3b led a strong absorption in the near-IR region corresponding to the formation of the stabilized dianionic species 3a(RED)(2-) and 3b(RED)(2-). An electrochromic analysis revealed the lower stability of the tetraanionic species 3a(RED)(4-..) and 3b(RED)(4-..), although the CV exhibited good reversibility. The mono(enediyne) systems 11a and 11b were also prepared for comparison. The electrochemical reduction of 11a and 11b did not exhibit good electrochemical reversibility by CV, but the electrochemical reduction led to a strong absorption in the near-IR region, similar to the formation of the stabilized dianionic species 3a(RED)(2-) and 3b(RED)(2-) in the bis(enediyne) systems. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

DOI： 10.1002/ejoc.200900743

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

Synthesis of [Ru(phenP)(3)](PF(6))(2), where phenP = phenanthrolinoporphyrin, has been achieved by the reaction of phenanthrolinoporphyrins with RuCl(3) for the first time. The phenP reacted with Ru(II) to form RuL(2)(phenP)(2+) complexes (L = 2,2&apos;-bipyridine or 1,10-phenanthroline), which were converted Into the dyads Ru-phenP(Zn) on treatment with zinc acetate.

DOI： 10.1021/ol901510e

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

Nitration of 4,7-ethanoisoindoles gave 1-nitro derivatives in moderate yields. Reduction of a nitro to amino group was successfully performed by sodium hydrosulfite in the case of ethyl 3-nitro-4,7-ethanoisoindole-1-carboxylate. The amino derivative was converted to benzylidenaminoisoindoles based on the retro Diels-Alder reaction. Their UV-vis spectra showed strong absorptions at 500-700 nm. (C) 2009 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2009.03.072

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：JAPAN SOCIETY APPLIED PHYSICS  

Organic thin-film transistors were successfully fabricated by the spin-coating method using a photo-precursor of pentacene, 6,13-dihydro-6,13-ethanopentacene-15,16-dione. After spin coating the soluble precursor, irradiation with visible light gave a pentacene film. A good mobility of 0.34 cm(2) V(-1) s(-1) and a high on/off ratio of 2.0 x 10(6) were achieved by treatment of the insulator surface with methyl silsesquioxane and by deposition of pentacene from the precursor with visible light irradiation (&gt;300 nm) and mild heat treatment (110-120 degrees C). In this case, small grains of pentacene crystals existed in the loosely ordered pentacene mesophase, in which pentacene molecules aligned vertically. Not only the grains of pentacene crystals but also the loosely packed pentacene phase played an important role in the field-effect transistor (FET) performance. (C) 2009 The Japan Society of Applied Physics

DOI： 10.1143/JJAP.48.051505

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Electrophilic ipso-substitution reactions between 1,3,6-tritert- butylazulcne (2) and several electrophilic reagents were examined. Friedel-Crafts and Vilsmeier reactions of 2 gave the corresponding ipso-substitution products in moderate to excellent yields. One of the ipso-substitution products, 1,6- di-tert-butyl-3-formylazulene (5), was converted in high yield into the synthetically more useful azulene derivative 1,6-di-tert-butylazulene (1) by decarbonylation on treatment with pyrrole in acetic acid. Treatment of 2 with N-[(trifluoromelhyl)su]fonyl] pyridinium trifluoromethanesulfonate (TPT) unexpectedly afforded 1- trifluoromethylthioazulene 10 and l(8H)-azulenone 11. Compound 2 also reacted with tetracyanoethylene (TCNE) to give an excellent yield of cycloaddition product 13, rather than the ipso-substitution reaction product. © Wiley-VCH Verlag GmbH &amp; Co. KGaA.

DOI： 10.1002/ejoc.200801253

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

Soluble precursors of beta-, meso-unsubstituted mono-, di- and tribenzoporphyrins were prepared by the reaction of dimethylbicyclo[2.2.2]octadiene-fused pyrrole with appropriate beta-free pyrroles. The retro Diels-Alder reaction of these precursors afforded the corresponding benzoporphyrins in quantitative yields.

DOI： 10.3987/COM-08-S(F)105

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：TAYLOR & FRANCIS LTD  

Acenaphtho[1,2-b]porphyrins (AcePs) were prepared by the [3 + 1] condensation method and their photochemical properties were investigated. The fluorescence spectra of the free-base AcePs in CHCl(3) showed two emission bands at 660 and 720 nm, whose intensity drastically changed depending on the excitation wavelength. However, those of zinc complexes did not show such a wavelength dependence and showed similar emission spectra by the excitation at various wavelengths. The fluorescence excitation spectra and quantum yields of the free-base AcePs in CHCl(3) showed the similar excitation wavelength dependence. This fact indicates that two electronic structures exist in the free-base AcePs and their fluorescence is emitted from one structure in higher quantum yield (lambda(EM) = 660 nm) and from the other in lower yield (lambda(EM) = 720 nm), respectively.

DOI： 10.1080/15421400902945378

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

The first facile syntheses of free-base di- and tetrabenzoporphycenes and their metal complexes; are reported. based on retro-Diels-Alder reactions of the corresponding bicyclo(2.2.2]octadiene-fused porphycenes. prepared by McMurray coupling of alpha,alpha&apos;-diformyldipyrrole. The photophysical and electrochemical properties are analyzed based on UV/Vis absorption. magnetic circular dichroism (MCD). and fluorescence emission. lifetime and quantum yield measurements, cyclic and differential pulse voltammetry (CV and DPV) and time-dependent DFT calculations based on B3LYP geometry optimizations. Benzoporphycenes are found to be prime candidates for future use in photodynamic therapy.

DOI： 10.1002/chem.200900755

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

The synthesis and spectroscopic properties of a series of boron-free meso-aryl-substituted [14]triphyrin(2.1.1) compounds containing either peripheral bicyclo[2.2.2]octadiene (BCOD) (2a-c) or benzene rings (3a-c) (aryl = phenyl. a, 4-fluorophenyl b, and 4-methylbenzoatephenyl c) are reported. These compounds represent the first examples of free-base contracted porphyrinoids with 14 TT-electron aromatic systems containing only the standard pyrrole and isoindoline moieties of the porphyrins and tetrabenzoporphyrins.

DOI： 10.1021/ja8068769

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

One of 5-alkenyl-15-alkynyl-porphyrin and 5,15-dialkynyl-porphyrin was prepared selectively by 2+2 acid-catalyzed condensation of bicyclo[2.2.2]octadiene-fused dipyrrylmethane and TMS propynal in the presence of BF(3) OEt(2) only by the choice of the solvent. The alkenyl group was expected to be obtained by a protonation followed by intramolecular 1,2-hydride transfer from methine position of porphyrinogen. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.05.115

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

Abstract

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

DOI： 10.1002/chin.200830061

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

Linearly pi-expanded novel tetraanthroporphyrins with and without aromatic rings at the meso-positions were prepared quantitatively for the first time from the corresponding precursors by a retro-Diels-Alder reaction.

DOI： 10.1021/ol8008842

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Several azulene-substituted thioketones, 1-thiobenzoylazulene (1a) and di(1-azulenyl) thioketone (2a) and their derivatives (1b and 2b-d) with alkyl substituents on each azulene ring, were prepared and their intramolecular pericyclization reaction was examined. The thioketones with a 3-alkyl substituent on each azulene ring exhibited the presumed pericyclization reaction under thermal and acid-catalyzed conditions, although the cases of the 1-azulenyl thioketones without the 3-alkyl substituents afforded a complex mixture under similar conditions. The intramolecular reaction following the intramolecular hydrogen transfer afforded the products 13b, 14b, and 14c. The products 13b and 14b were converted into the corresponding cations 18(+) and 19(+), which have structural similarity with that of the phenalenyl cation. These cations exhibited the expected two-step reduction waves upon CV, although the ESR analysis revealed that the neutral radical state did not have the presumed high stability.

DOI： 10.1021/jo702309b

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

This paper describes the preparation of dimethylbicyclo[2.2.2]octadiene-fused porphyrins as extremely soluble precursors of tetrabenzoporphyrins and thermal conversion of the precursors to tetrabenzoporphyrins. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2008.01.014

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

Multistep thermal fragmentation of quadruply bicyclo[2.2.2]octadiene-fused porphyrins giving tetrabenzoporphyrins was examined in detail. After the first extrusion of an ethylene molecule from the porphyrin derivative, the opposite bicyclo[2.2.2]octadiene moiety preferentially underwent the second retro-Diels-Alder reaction to give an opp-dibenzoporphyrin derivative rather than an adj-dibenzoporphyrin derivative. These two benzoporphyrin derivatives then decomposed to give a tribenzoporphyrin derivative in similar rates. The temperature regions of these fragmentations could not be distinguished by thermogravimetric analysis. In contrast, the third and the fourth fragmentations obviously occurred stepwise. There was a temperature region where the tribenzoporphyrin derivative preferentially existed. In the case of the 21,23-dithiaporphyrin derivative, opp-21,23-dithiadibenzoporphyrin, possessing benzo moieties fused at the pyrrole parts of the core-modified porphyrin chromophore was predominantly formed during the fragmentation. In the case of the 21-thiaporphyrin derivative, an ethylene molecule was extruded selectively from the bicyclo[2.2.2]octadiene moiety adjacent to the thiophene part to give 21-thiabenzo[q]phyrin and then 21-thiabenzo[g,q]porphyrin derivatives. In these cases, the last ethylene extrusion also occurred very slowly. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

DOI： 10.1002/ejoc.200700711

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

Soluble precursors of 2,3-naphthalocyanine (Nc) and phthalocyanine (Pc) were prepared and were converted into insoluble semiconducting thin films of Pc and Nc by heating after fabrication via spin-coating.

DOI： 10.1039/b811674a

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

The optical spectra of a series of core-modified tetrabenzoporphyrins were analyzed to determine the effects of core modification, ligand folding, and partial benzo substitution at the ligand periphery on the electronic structure by using magnetic circular dichroism (MCD) and NMR spectroscopy, X-ray crystallography, cyclic and differential pulse voltammetry, and TD-DFT calculations. Planar 21-carba-, 21-thia-, 21,23-dithia-, and 21-oxa-23thiatetrabenzo[b,g,l,q]porphyrins reported previously were studied together with the previously unreported 21-oxa- and 21-carba-23-thiatetrabenzo[b,g,l,q]porphyrins. The optical properties of these compounds are compared to those of tetrabenzo[b,g,l,q]-, 5,.10,15,20-tetraphenyl-, 5,10,15,20-tetraphenyltetrabenzo[b,g,l,q]-21-thia-, 5,10,15,20-tetraphenyltetrabenzodithia-, 5,10,15,20-tetraphenyldibenzo[g,q]21,23-dithia-, 5,10,15,20-tetraphenyldibenzo[b,t]-21,23-ditliia-, 5,10,15,20tetraphenyltribenzo[g,q]-1-21-thia-, and 5,10,15,20-tetraphenylbenzo[b]-21-thia- porphyrins. Michl&apos;s perimeter model and Gouterman&apos;s four-orbital model are used to conceptualize the results and to account for red shifts commonly observed in the spectral bands of nonplanar porphyrinoids.

DOI： 10.1002/chem.200701611

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Language：English   Publisher：ROYAL SOC CHEMISTRY  

Solution processable organic semiconducting small molecules are desirable for the manufacture of low-cost, large-area electronic products on flexible substrates. This article provides an overview of recent progress in OFETs based on solution processable small molecules that can be converted to insoluble organic semiconducting materials on films by thermal or photochemical removal of leaving groups after fabrication of the film.

DOI： 10.1039/b719964c

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Two new 8-(4-dimethylaminophenyl) substituted boron-dipyrromethene (BDP) dyes: 1,2,6,7-tetraethyl-4,4-difluoro-3,5-dimethyl8-(4-dimethylaminophenyl)-4-bora-3a,4a-diaza-s-indacene (5) and 4,4-difluoro-1,2,3,5,6,7-hexamethyl-8-(4-dimethylaminophenyl)4-bora-3a,4a-diaza-s-indacene (6) have been synthesized and their crystal structures are determined by X-ray diffraction analysis. The torsion angles of 8-phenyl ring and the indacene plane are 79.61 degrees for 5 and 87.56 degrees for 6, respectively. The absorption and steady-state fluorescence properties in different solvents have been investigated. The fluorescence quantum yields of the two dyes are lower in more polar solvents, which can be ascribed to the intramolecular charge transfer from the aniline to the BDP unit. Protonation of the aniline moiety at low pH in MeOH-H2O (1:1 v/v) solution causes a large fluorescence enhancement. The pk(a) values calculated from the pH dependent fluorescence emission spectra are 3.14 for 5 and 3.09 for 6, respectively. They are suitable as pH probes excitable with visible light. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.molstruc.2006.05.014

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

Mg complex of phthalocyanine fused with bicyclo[2.2.2]octadiene (BCOD) units is prepared by the reaction of BCOD-fused phthalonitrile with Mg(OPr)(2) in PrOH at 100 degrees C overnight in 42% yield. Subsequent heating the product at 250 degrees C results in clean formation naphthalocyanine via the retro Diels-Alder reaction. An attempt to the synthesis of BCOD-fused tetraazaporphyrin by the similar cyclization of the Diels-Alder adduct of dicyanoacetylene with 1,3-cyclohexadiene was unsuccessful.

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC PORPHYRINS & PHTHALOCYANINES  

Tetrabenzoporphyrin films on indium-tin-oxide electrodes were prepared by continuous spin-coating of indium-tin-oxide electrodes with a soluble precursor, tetrabicyclo[2.2.2]octadiene-fused porphyrin, and subsequent thermal conversion of the precursor to tetrabenzoporphyrin by annealing the modified electrodes. When the tetrabenzoporhyrin-modifled indium-tin-oxide working electrode was irradiated in a three-electrode system, using Pt as a counter electrode and Ag/Ag+ as a reference electrode in the presence of hexyl viologen as an electron acceptor, a cathodic photocurrent was observed. A double layer structure consisting of tetrabenzoporphyrin and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) films and a triple layer structure consisting of tetrabenzoporphyrin; a mixture of tetrabenzoporphyrin and PCBM; and PCBM films were also prepared on indium-tin-oxide electrodes by repeated spin coating. The incident photon to photocurrent efficiency values of up to 6.8% were obtained for the triple layer structure, in which the mixed layer contained tetrabenzoporphyrin and PCBM molecules in. a, 7:3 ratio. Action-spectra of the-triple layer structure showed that visible light from 380 to 700 nm sensitized the system for photocurrent generation. Copyright (C) 2007 Society of Porphyrins & Phthalocyanines.

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Diels-Alder reaction of ethynyl p-tolyl sulfone with 1,3-dienes gave the corresponding tosyl-1,4-cyclohexadienes. The resulting adducts could be converted into 4,7-dihydro-2H-isoindole derivatives including bicyclo[2.2.2]ocatadiene(BCOD)-fused pyrrole as an isoindole equivalent. © 2006 The Japan Institute of Heterocyclic Chemistry.

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

A diketone precursor of air-stable bis-2-thienyl-2,6-anthracene was prepared and quantitatively converted to the target acene by photoirradiation of the n-pi* absorption both in solution and as a film, in air. (c) 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2006.08.013

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Language：Chinese   Publishing type：Research paper (scientific journal)   Publisher：CHINESE CHEMICAL SOCIETY  

Two new exocyclic ring-fused boron-dipyrromethene (BDP) dyes with benzo crown ether subunit at meso-position were prepared. Their spectroscopic and electrochemical properties were investigated. The introduction of the electron withdrawing ester groups to the chromophore makes compound 2 to be a very sensitive fluorescent probe for Na+ analysis.

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

A series of meso-tetraaryl porphyrins with fused phenanthrene rings have been synthesized from boron trifluoride-catalyzed Lindsey condensation of phenanthro[9, 10-c]pyrrole with various para-substituted arylaldehydes at low temperature. Their structures were characterized by UV-vis, H-1 NMR, and mass spectroscopies. The UV-vis spectra of these compounds showed remarkable bathochromic shift of the Soret band to the wavelength around 577 nm and Q-bands into the near-infrared region. (c) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2005.11.162

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Benzoporphyrins fused with acenaphthylene or fluoranthene (3) and (4) were prepared by the condensation of bicyclo[2.2.2]octadiene(BCOD)-fused tripyrrane (5) with appropriate pyrrole dialdehydes (13) or (14) and the subsequent retro Diels-Alder reaction. The absorptions of these new porphyrins were very intense at both Soret and Q bands, which might be useful as organic dyes for solar cells.

DOI： 10.3987/COM-05-S(T)23

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

5-Alkenyl-15-alkynylporphyrins have been obtained unexpectedly by [2 + 2] acid-catalyzed condensation of dipyrrylmethane and TMS propynal in addition to 5,15-dialkynylporphyrin, and the unsymmetrical porphyrin can be converted to a butadiyne-linked dimer by selective desilylation of the alkynyl TMS.

DOI： 10.1039/b513848e

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SOC PORPHYRINS & PHTHALOCYANINES  

Soluble tetra(pyrazino)tetraazaporphyrin was synthesized by the reaction of bicyclo[2.2.2]octadiene-fused dicyanopyrazine. The retro Diels-Alder reaction of the soluble tetra(pyrazino)tetraazaporphyrin gave a tetra(quinoxalino)tetraazaporphyrin in quantitative yield. Copyright (c) 2006 Society of Porphyrins & Phthalocyanines.

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

A novel alpha-diketone precursor of pentacene, 6,13-dihydro-6,13-ethanopentacene-15,16-dione, was prepared and converted successfully to pentacene in 74% yield by photolysis of the precursor in toluene: Irradiation of the diketone solution in toluene with light of 460 nm under an Ar atmosphere caused the solution to change from yellow to fluorescent orange-pink within a few minutes, after which, purple precipitates appeared. After 35 min, the solution changed to colorless and the purple precipitates were filtered to give pentacene in 74% yield. By contrast, in the presence of oxygen, the color of the solution changed from yellow to pale yellow., and only 6,13-endoperoxide of pentacene was quantitatively obtained. The rate of the reaction upon photolysis was measured by observing the decay of n-pi* absorption of the precursor at 460 nm, and was found to be similar in both the presence and absence of oxygen. Therefore, the photoreaction of the alpha-diketone precursor seemed to occur via the singlet excited state. Because the T-T absorption of pentacene was observed upon photolysis of the precursor in the nanosecond transient absorption measurement under an Ar atmosphere, the excited triplet state of the pentacene generated singlet oxygen by sensitization, and it reacted with the ground-state pentacene to give the 6,13-endoperoxide. The alpha-diketone deposited on glass was also converted successfully to pentacene film by photoirradiation. In addition, diketone precursors of a mixture of 2,8- and 2,9-di-bromopentacene and 2,6-trianthrylene were also prepared and their photoconversion was performed.

DOI： 10.1002/chem.200500564

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6,13-Dihydro-6,1 3-ethanopentacene-15,16-dione gave pentacene efficiently both in solid and in solution by irradiation of light. (C) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2005.01.157

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

A bicyclo[2.2.2]octadiene-fused tripyrrane was synthesized as a first versatile reagent for the preparation of pi-expanded heteroporphyrins. The reaction of the tripyrrane with 1,3-diformylindene and azulene-1,3-dicarbaldehyde afforded the corresponding heteroporphyrins. which were easily converted into tetrabenzocarbaporphyrin and tribenzoazuliporphyrin by retro Diels-Alder reaction. (C) 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2004.05.041

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

This paper describes an efficient preparation of 2-azulenylboronate (6) starting from 2-iodoazulene by halogen-metal exchange reaction using n-BuLi and subsequent quenching with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The boronate 6 has been found to undergo Pd-catalyzed Miyaura-Suzuki cross-coupling reaction with a range of aryl bromides including aromatic poly bromides utilizing Pd-2(dba)(3)-P(t-Bu)(3) as a catalyst and establishes a strategy to produce novel poly(2-azulenyl)benzenes, some of which are found to be insoluble in common organic solvents, however. The redox behavior of 2-arylazulenes and poly(2-azulenyl)benzenes was examined by cyclic voltammetry (CV) and compared with those of 6-azulenylbenzene derivatives reported previously. (C) 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2004.04.057

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

Successful synthesis of a series of highly conjugated porphyrin analogues, including thia-, dithia- and oxathia-tetrabenzoporphyrins, and their optical properties are reported.

DOI： 10.1039/b311879g

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

Amination of 2-substituted azulene was carefully examined using several types of amines, and the scope and limitation of substrates and reagents in these direct nucleophilic aminations were found. The synthesis of 2-aminoazulenes was successfully achieved by the reaction of 2-bromoazulene with several amines via palladium-catalyzed amination. (C) 2003 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2003.08.048

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

Preparation and cycloaddition reaction of novel azulene-substituted N-sulfinylamines I and 2 are reported. The influence of the -N=S=O group on the UV-vis and NMR spectra of the azulene ring to which it is bonded is discussed. X-ray crystal analysis of 1 revealed the syn-configuration and the twisted structure of the N-sulfinylamine moiety. The synthetic utility of I and 2 have been explored by the cycloaddition reaction to afford novel azulene-substituted heterocycles under high-pressure conditions. We also described herein the synthesis and some proper-ties of related 2-azulenylisothiocyanate. (C) 2003 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4020(03)00637-9

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

2-Azulenyl trifluoromethanesulfonate was prepared by the reaction of 2-hydroxyazulene with trifluoromethanesulfonic anhydride in the presence of triethylamine as a base. Under the use of pyridine, 1-trifluoromethane-sulfonylpyridinium trifluoromethanesulfonate further reacted with 2-azulenyl trifluoromethanesulfonate to give 1-(1-trifluoromethanesulfonyl-1,4-dihydropyridin-4-yl) azulenyl trifluoromethanesulfonate. Moreover, we found that azulenes also reacted with 1-trifluoromethanesulfonylpyridinium trifluoromethanesulfonate to give 4-(1-azulenyl)1,4- dihydropyridine derivatives and 6-(1-azulenyl)-1-trifluoromethanesulfonyl-1-aza-hexa-1,3,5-triene depending on the reaction conditions. 2-Azulenyl trifluoromethanesulfonate was converted finally into the parent azulene in excellent yield by palladium-catalyzed reduction using formic acid as a reducing reagent.

DOI： 10.1039/b212484j

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

The first versatile organometallic reagents derived from azulenes, i.e.. 6-(tri-n-butylstannyl)azulene (1a) and its, 1,3-diethoxycarbonyl derivative (1b), have been prepared by Pd(o)-catalyzed direct stannylation of 6-bromoazulenes, with bis(tri-n-butyltin). We demonstrate the utility of the reagents in the Stille cross-coupling reaction with aryl.acetyl and azulenyl halides to afford 6-aryl-, 6-acyl- and bi-azulenes in good yield. Furthermore. the methodology was applied to the synthesis of poly(azulen-6-yl)benzene derivatives. The reaction of 1b with 1.4-di-, 1,3,5-tri-. 1,2,4,5-tetra- and hexabromobenzenes afforded 1.4-di-, 1,3,5-tri-, 1,2,4,5-tetra-, 1,2,4-tri- and 1,2,3,5-tetra(azulen-6-yl)benzene derivatives (18, 20, 22, 24 and 25). The redox behavior of 18 and 22 was examined by cyclic voltammetry (CV) and compared with those of 20 and 24 reported previously. In contrast to the three-step reduction of 20, the compound 18 exhibited a reversible one-step two-electron reduction wave at - 1.30 V Upon CV, which revealed the formation of a closed-shell dianion. The four azulen-6-yl substituents on benzene in a 1,2,4,5 relationship increased electron-accepting properties because of the formation of a closed-shell dianion stabilized by four azulen-6-yl groups. As expected, the compound 22 exhibited a color change during the electrochemical reduction. However, the reverse oxidation did not regenerate the spectrum of 22 due to the low stability of the presumed dianionic species under the conditions of the UV-vis measurement.

DOI： 10.1039/b203836f

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

The first versatile organometallic reagents of azulenes, 6-(tri-n-butylstannyl)azulenes, have been prepared by a Pd(0)-catalyzed direct stannylation of 6-bromoazulenes with bis(tri-n-butyltin). We demonstrate herein the utility of the reagents in the Stille cross-coupling reaction with aryl and azulenyl halides to afford 6-aryl- and biazulenes in good yield. (C) 2002 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(01)02347-4

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

The titled stable monocations, di(1-azulenyl)(2- and 3-thienyl)methyl cations 7a,b and 8a,b and dications composed of two di( 1-azulenyl)methylium units connected with 2,5-thiophenediyl and 2,5-thieno[3,2-b]thiophenediyl spacers 9a,b and 10a,b were prepared by hydride abstraction of the corresponding methane derivatives. These mono- and dications 7a,b, 8a,b, 9a,b, and 10a,b showed high stability with large pK(R)(+) values. The values of monocations 7a,b and 8a,b were 11.2-11.8 +/- 0.1 and 11.4-12.4 +/- 0.1, respectively. Two cation units in dications 9a,b and 10a,b were neutralized via one step at the pH of 11.1-11.7 +/- 0.1, which corresponds to the average of the pK(R)(+) values of the dications and half-neutralized monocations. Electrochemical behavior of 7a,b, 8a,b, ga,b, and 10a,b was examined by cyclic voltammetry (CV). Formation of the thienoquinoid products 18a,b and 19a,b from 9a,b and 10a,b was characterized by UV-vis spectroscopy under electrochemical reduction conditions. Chemical reduction of 9a,b and 10a,b with Zn powder in acetonitrile afforded 18a,b and 19a,b as deep-colored crystals, which exhibited rather high electron-donating ability.

DOI： 10.1021/jo001709r

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

Described herein is a cobalt-mediated cyclooligomerization of mono- and di(6-azulenyl)acetylenes to afford 1,3,5- and 1,2,4-tri(b-azulenyl)benzene derivatives and (eta (5)-cyclopentadienyl)[tetra- and di(6-azulenyl)cyclobutadiene]cobalt complexes. The redox behavior of these novel tri(6-azulenyl)benzene derivatives and [tetra- and di(6-azulenyl)cyclobutadiene]cobalt complexes examined by cyclic voltammetry is also described. (C) 2001 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(00)02187-0

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

Diazuleno[2,1-b:1,2-e]pyridines (2a and 2b) were prepared in one pot by the reaction of 2-aminoazulene (1a) with paraformaldehyde or benzaldehyde in moderate yields. Bis(2-amino-3-ethoxycarbonyl-1-azulenyl)methane (8a) was formed by the reaction of ethyl 2-aminoazulene-1-carboxylate (1b) with 1/2 molar amount of paraformaldehyde. Treatment of 8a with paraformaldehyde at room temperature afforded three heterocyclic compounds (9, 10, and 11). When 2-acetylaminoazulenes (1c and 1d) were used for this reaction, bis(2-acetylamino-1-azuleny)methanes (8b and 8c) were exclusively formed.

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DOI： 10.1021/jo010540u

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

1,2-Di(6-azulenyl)tetraphenylbenzenes and (6-azulenyl)pentaphenylbenzenes were synthesized by Diels-Alder reaction of di(6-azulenyl)acetylenes and 6-(phenylethynyl)azulenes with tetraphenylcyclopentadienone. Mono(6-azulenyl)benzenes exhibited a reduction wave upon cyclic voltammetry (CV). In contrast to the benzene derivatives, di(6-azulenyl)benzenes showed a two-step reduction wave at similar potential region upon CV, which revealed the formation of dianions stabilized by 6-azulenyl substituents under electrochemical reduction conditions. (C) 2000 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(00)01445-3

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DOI： 10.1016/S0040-4020(99)00280-X

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

The title carbocation, generated from 1,1-ethylene-1,6-dihydroazulene and trityl tetrafluoroborate in deuterated acetonitrile at - 20 degrees C, was characterized by means of lcw temperature NMR spectroscopy, and was found to undergo expansion of the cyclopropane ring at elevated temperature and to react with nucleophiles to give the addition products at the cyclopropane methylene carbon.

DOI： 10.1246/cl.1997.1011

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Publishing type：Book review, literature introduction, etc.  

© 2018 Society of Synthetic Organic Chemistry. Extension of the π-system of porphyrins has attracted the interest of many chemists for applications such as light-emitting displays, organic thin-film electronics, and photosensitizers as a near-infrared dye. Herein we report our recent works on synthesis of aromatic ring-fused porphyrins and ring-expanded porphyrins with no meso-bridges. Porphyrins linked with aromatic ring through bicyclo[2.2.2] octadiene were prepared via the tetramerization and [3+1] porphyrin synthesis methods. The subsequent thermal conversion afforded ring-annelated porphyrins. Core-modified benzoporphyrins and π-extended BODIPYs were also obtained by the similar retro Diels-Alder strategy. Ring-expanded porphyrins with no meso-bridges, cyclo [n] pyrroles (n = 8 and 10), were selectively synthesized by using an oxidative coupling of the corresponding 2,2′-bipyrrole in the presence of appropriate template dianions. These octaphyrins and decaphyrin exhibited a markedly red-shifted strong L band at ca. 1,000-2,000 nm.

DOI： 10.5059/yukigoseikyokaishi.76.690

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