担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/acs.orglett.2c04173

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

The development of highly electron-accepting π-systems is a fundamentally challenging issue despite their potential applications as various functional materials.

DOI： 10.1039/d2sc05992d

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

In this study, we compare a bowl-shaped aromatic hydrocarbon with internal methoxy groups to related derivatives with hydrogen, methyl, and anisyl groups, evaluating their electron-accepting properties, electronic absorption spectra, and fullerene-binding behavior.

DOI： 10.1039/d3qo01661g

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/ejoc.202200770

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ejoc.202200770

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

DOI： 10.1246/cl.210754

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/chem.202103647

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202103647

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

The model molecule, bis-ANI (consisting of two naphthalimide moieties) was studied to better understand the process of charge separation. It is found that the central amino linker facilitates the formation of a charge separation state in bis-ANI.

DOI： 10.1039/d2cp00295g

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

We report the synthesis and properties of acridino[2,1,9,8-klmna]acridine bisimide (AABI), a nitrogen-doped anthanthrene with two imide functionalities. AABI exhibits excellent electron affinity as evident by its low-lying LUMO level (-4.1 eV vs. vacuum). Single-electron reduction of one AABI derivative afforded the corresponding radical anion, which was stable under ambient conditions. Photoconductivity measurements suggest that the intrinsic electron mobility of an N-phenethyl AABI derivative obeys a band-transport model. Accordingly, an electron mobility of 0.90 cm(2) V-1 s(-1) was attained with the corresponding single-crystal organic field-effect transistor (OFET) device. The vacuum-deposited OFET device consisting of a polycrystalline sample exhibited high electron mobility of up to 0.27 cm(2) V-1 s(-1) even in air. This study demonstrates that dual incorporation of both imide substituents and imine-type nitrogen atoms is an effective strategy to create novel electron-deficient pi-systems.

DOI： 10.1002/anie.202102708

Web of Science

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The synthesis and properties of dinaphthotropone bisimide (DNTrBI) and dinaphthocycloheptatriene bisimide (DNCHepBI) are described. Their molecular design is conceptually based on the insertion of a carbon atom into a perylene bisimide (PBI) core. These molecules adopt non-planar structures due to the presence of a seven-membered ring. The PBI derivative into which a carbonyl group was inserted (DNTrBI) immediately underwent nonradiative decay and/or intersystem crossing in its excited state. The PBI derivative into which a methylene group was inserted (DNCHepBI) was susceptible to deprotonation on account of the two electron-withdrawing naphthalene monoimide units. Subsequent aerobic oxidation resulted in the formation of a C-C bond at the central methylene unit, thus affording a sigma-dimer. The formation of this C-C bond is dynamically redox-active, i.e., electron injection into the sigma-dimer almost quantitatively regenerated the deprotonated DNCHepBI.

DOI： 10.1002/anie.202104882

Web of Science

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

V-shaped pi-systems are attractive research targets in organic chemistry and materials science. Our group has recently demonstrated that the conceptual insertion of a heteroatom into a perylene bisimide (PBI) core is an effective guideline for the design of non-planar PBI derivatives. Here we report the synthesis and properties of dinaphtho[1,8-bc:1 ',8 '-fg][1,5]dithiocine bisimide (DNDTBI), which represents a doubly sulfur-inserted PBI derivative. The X-ray diffraction analysis revealed that DNDTBI adopted a V-shaped structure with a dihedral angle of 67 degrees. DNDTBI exhibited higher electron-donating ability than singly sulfur-inserted PBI derivative owing to the antibonding interaction between the two neighboring sulfur atoms. The inversion barrier of the flipping motion of DNDTBI was ca. 30 kcal mol(-1), indicating the rigid nature of the V-shaped structure.

DOI： 10.1002/ajoc.202000722

Web of Science

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：NATURE PUBLISHING GROUP  

Carbon and hydrogen are fundamental components of organic molecules and a fascinating plethora of functions can be generated using these two elements. Yet, realizing attractive electronic structures only by using carbon and hydrogen remains challenging. Herein, we report the synthesis and properties of the C-70 fragment as-indaceno[3,2,1,8,7,6-ghijklm]terrylene, which exhibits near-infrared (NIR) absorption (up to ca. 1300nm), even though this molecule consists of only 34 carbon and 14 hydrogen atoms. A remarkably small highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap is confirmed by electrochemical measurement and theoretical calculations. Furthermore, as-indacenoterrylene is stable despite the absence of peripheral substituents, which contrasts with the cases of other NIR-absorbing hydrocarbons such as diradicaloids and antiaromatic molecules. The results of this study thus offer fundamental insights into the design of hydrocarbons with a small band gap. The synthesis of hydrocarbons with attractive electronic structures remains challenging. Here, the authors describe the synthesis and properties of the C70 fragment as-indaceno[3,2,1,8,7,6-ghijklm]terrylene, which exhibits near-infrared (NIR) absorption.

DOI： 10.1038/s41467-020-17684-6

Web of Science

その他リンク： http://www.nature.com/articles/s41467-020-17684-6

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/jacs.0c04096

Scopus

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.1021/jacs.9b09556

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

We have prepared four 4-aminonaphthalene monoimide derivatives and examined the aggregation-induced emission (AIE) properties. A nitrogen-bridged dimer is AIE-active and exhibits bright green emission with a high quantum yield in the solid state. The X-ray diffraction analysis suggests that key to the bright luminescence is the favorable crystal packing dominated by CH/p interaction. The late-stage cyanation of the dimer tuned its AIE color from green to orange.

DOI： 10.1021/acs.orglett.9b03699

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.20180103

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

Singly and doubly 1,2-phenylene-inserted NiII porphyrin arch-tape dimers 3 and 9 were synthesized from the corresponding β-to-β 1,2-phenylene-bridged NiII porphyrin dimers 5 and 11 via Ni0-mediated reductive cyclization and DDQ/Sc(OTf)3-promoted oxidative cyclization as key steps, respectively. Owing to the fused eight-membered ring(s), 3 showed a more contorted structure than those of previously reported arch-tape dimers 2 a and 2 b possessing a fused seven-membered ring. Furthermore, 9 displayed much larger molecular contortion. As the molecular contortion increases, the Q band of the absorption spectrum becomes more red-shifted and the electrochemcial HOMO–LUMO gap becomes smaller, reaching at 1294 nm and 0.77 eV in 9, respectively. The effect of molecular contortion on the electronic properties was studied by means of DFT calculations.

DOI： 10.1002/anie.201802494

Web of Science

Scopus

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

Incorporation of planarized heteroatom(s) onto the porphyrin periphery is an effective approach to create porphyrin-based functional materials. In the last three decades, such an "embedding heteroatom" strategy has been actively explored in order to realize attractive electronic, optical, and electrochemical properties. This review aims to cover a variety of synthetic methodologies that have been developed for the construction of heteroatom-embedded porphyrins. Moreover, we also summarize their structure-property relationships as well as possible applications in various research fields including artificial photosynthesis, molecular engineering, organic electronics, and bioimaging.

DOI： 10.1039/c7dt02815f

Web of Science

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

Porphyrin tapes possessing meso-meso beta-beta beta-beta triple direct linkages have been targets of extensive studies because of their fully conjugated characteristic pi-electronic networks. In this paper, we report porphyrin arch tapes that bear additional carbonyl group(s) or methylene group(s) inserted between one of the beta-beta linkage(s) of the porphyrin tapes. The carbonyl-inserted porphyrin arch-tapes were efficiently synthesized by double fusion reactions of beta-to-beta carbonyl-bridged porphyrin oligomers with DDQ and Sc(OTf)(3), and were converted to the methylene-bridged porphyrin arch-tapes via Luche reduction with NaBH4 and CeCl3 followed by ionic hydrogenation with HBF4 center dot OEt2 and BH3 center dot NEt3. While the conventional porphyrin tapes display rigid and planar structures and low solubilities, these porphyrin arch-tapes show remarkably contorted structures, flexible conformations, and improved solubilities because of the presence of the incorporated seven-membered ring(s). Interestingly, the methylene inserted arch-tapes exhibited conjugative electronic interactions that were comparable to those of porphyrin tapes probably owing to through-space interaction in the contorted conformations. The carbonyl-inserted arch-tapes displayed distinctly larger conjugative interactions owing to an active involvement of the carbonyl group(s) in the electronic conjugation. A similar trend was observed in the nonlinear optical properties, as evidenced by their two-photon absorption cross sections. Furthermore, as a benefit of the contorted structures, these porphyrin arch-tapes can catch C-60 fullerene effectively. Naturally, the electron-rich methylene-bridged arch-tapes exhibited larger association constants than the electron-deficient carbonyl-bridged arch-tapes. Among these arch-tapes, a methylene-bridged syn-Ni(II) porphyrin trimer recorded the largest association constant of (1.5 +/- 0.4) X 10(7) M-1 in toluene at 25 degrees C.

DOI： 10.1021/jacs.7b05332

Web of Science

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

The synthesis and characterization of meso-to-meso Pt-II-bridged Ni-II-porphyrin dimers 5-7 are reported herein. A boron-platinum exchange reaction of meso-pinacolatoborylporphyrin 8 with Pt(cod) Cl-2 afforded the cod-coordinated meso-to-meso Pt-II-linked cis-dimer 5, which was subsequently converted to the 1,3-bis(diphenylphosphino) propane (DPPP)-coordinated cis-dimer 6 and the PPh3-coordinated trans-dimer 7 upon treatment with DPPP and PPh3, respectively. On the other hand, a reaction of 5 with tri-tert-butylphosphine induced reductive elimination to give the meso-meso directly linked diporphyrin 9. Comparative studies of these Pt-II-bridged Ni-II-porphyrin dimers were conducted by UV/Vis absorption spectroscopy, electrochemical studies, and theoretical calculations. In the course of these studies, we found that cis-dimers 5 and 6 underwent an unprecedented reductive elimination to give the mesomeso linked dimer 9 upon chemical or electrochemical one-electron oxidation, while trans-dimer 7 was stable under such conditions.

DOI： 10.1039/c7qo00093f

Web of Science

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

Oxidative fusion reactions of meso-phenoxazino Ni(II) porphyrin were found to be temperature dependent, giving rise to either a doubly phenylene-fused product at room temperature or a singly phenoxazine-fused product at 70 degrees C. The latter was further oxidized to a doubly phenoxazine-fused Ni(II) porphyrin, which was subsequently converted to the corresponding free base porphyrin and Zn(II) porphyrin. Compared to previously reported diphenylamine-fused porphyrins that displayed a molecular twist, doubly phenoxazine-fused porphyrins exhibited distinctly different properties owing to their highly planar structures, such as larger fluorescence quantum yields, formation of an offset face-to-face dimer both in solution and the solid state, and the generation of a mixed-valence p-radical cation dimer upon electrochemical oxidation. One-electron oxidation of the phenoxazine-fused Ni(II) porphyrin with Magic Blue gave the corresponding radical cation, which was certainly stable and could be isolated by separation over a silica gel column but slowly chlorinated at the reactive beta-positions in the solid state. This finding led to us to examine beta, beta'-dichlorinated phenoxazine-fused and diphenylamine-fused Ni(II) porphyrins, which, upon treatment with Magic Blue, provided remarkably stable radical cations to an unprecedented level. It is actually possible to purify these radical cations by silica gel chromatography, and they can be stored for over 6 months without any sign of deterioration. Moreover, they exhibited no degradation even after the CH2Cl2 solution was washed with water. However, subtle structural differences (planar versus partly twisted) led to different crystal packing structures and solid-state magnetic properties.

DOI： 10.1039/c6sc02721k

Web of Science

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

Abstract

Norcorrole Ni(II) complexes have recently received considerable attention because they are readily accessible antiaromatic molecules. Their high stability under ambient conditions and ease of synthesis have enabled the exploration of the intrinsic properties of antiaromatic molecules. Here, we report the synthesis and properties of meso–meso singly linked porphyrin‐norcorrole hybrids and a triply linked porphyrin‐norcorrole hybrid. The singly linked and triply linked porphyrin‐norcorrole hybrids were fully characterized, including an X‐ray structural analysis. Due to their orthogonal conformation, the singly linked hybrids maintain the individual electronic properties of their porphyrin and norcorrole subunits, while the triply linked hybrid shows a significantly smaller electrochemical HOMO–LUMO gap (0.45 eV) than that of Ni(II) dimesitylnorcorrole (1.08 eV). Furthermore, the triply linked hybrid exhibits singlet diradical characteristics, as confirmed by VT NMR, ESR, and SQUID experiments.

DOI： 10.1002/anie.202401233

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

DOI： 10.1002/anie.202300437

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202300437

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：World Scientific Pub Co Pte Ltd  

We prepared a free-base 10,20-diphenyl-5,15-diazaporphyrin and its Ni(II), Cu(II), Pd(II), and Pt(II) complexes. These molecules uniformly form an infinite one-dimensional [Formula: see text]-stacking array in the solid state. The four-fold intermolecular hydrogen bonding interactions between the meso-nitrogen atom of the diazaporphyrin core and the ortho-hydrogen atom of the phenyl substituent dominate the crystal packing arrangement. The present study revealed that the meso-nitrogen atom of diazaporphyrins would be used as an inherent hydrogen bonding acceptor to construct supramolecular assemblies.

DOI： 10.1142/s1088424622500997

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：World Scientific Pub Co Pte Ltd  

Recently, norcorrole Ni(II) complexes have received much attention because they exhibit peculiar solid-state structures and fascinating electronic properties originating from their distinct antiaromatic character. In this work, we have prepared a norcorrole Ni(II) complex with 5-hexylthien-2-yl substituents at the meso-positions, of which the antiaromatic nature was evaluated by ¹H NMR analysis as well as NICS and ACID calculations. The X-ray diffraction analysis elucidated its molecular structure and crystal packing arrangement. Crystal packing structures of Ni(II) meso-di(5-methylthien-2-yl)norcorrole and Ni(II) meso-di(5-hexylthien-2-yl)norcorrole were markedly different. The latter provided a polar crystal because of the unidirectional alignment of 5-hexylthien-2-yl groups in the solid state.

DOI： 10.1142/s1088424622500730

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/jacs.2c08795

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Elsevier {BV}  

DOI： 10.1016/j.xcrp.2022.101045

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

The synthesis of Pd(II) and Cu(II) 10-azacorroles with a meso-NH group has been achieved through the thermal extrusion of one nitrogen atom from the corresponding diazacorrphycene metal complexes. We also found that oxidation of the Cu(II) 10-azacorrole complex afforded another type of copper 10-azacorrole with an imine moiety. The structural, magnetic, and electrochemical properties of these compounds were investigated to disclose the nature of two types of copper 10-azacorroles.

DOI： 10.1246/cl.210777

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：The Chemical Society of Japan  

DOI： 10.1246/cl.210715

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

DOI： 10.1002/anie.202114230

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202114230

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

5,15-Diazaporphyrin appended with d-mannose moieties was prepared through Suzuki–Miyaura cross-coupling reaction and S_N2 alkylation.

DOI： 10.1039/d2ob01410f

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

DOI： 10.1002/anie.202109003

その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.202109003

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

Three-dimensional aromaticity arising from the close stacking of two antiaromatic π-conjugated macrocycles has recently received considerable attention. Here, a cyclophane consisting of two antiaromatic Ni(II) norcorrole units tethered with two flexible alkyl chains was synthesized. The norcorrole cyclophane showed crystal polymorphism providing three different solid-state structures. Surprisingly, one of them adopted an aligned face-to-face stacking arrangement with negligible displacement along the slipping axis. Although the exchange repulsion between two π-clouds should be maximized in this orientation, the π–π distance is remarkably close (3.258 Å). Three-dimensional aromaticity in this conformation has been supported experimentally and theoretically as evidenced by small bond length alternations as well as the presence of a diatropic ring current. An analogous cyclophane with two aromatic Ni(II) porphyrin units was prepared for comparison. The porphyrin cyclophane exhibited a slipped-stacking conformation with a larger displacement (2.9 Å) and a larger interplanar distance (3.402 Å) without noticeable change of the aromaticity of each porphyrin unit. In solution, the norcorrole cyclophane forms a twist stacking arrangement with effective interplanar orbital overlap and exists in an equilibrium between stacked and nonstacked structures. Thermodynamic parameters of the stacking process were estimated, revealing an inherently large attractive interaction operating between two norcorrole units, which has been further supported by energy decomposition analysis.

DOI： 10.1021/jacs.1c04348

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

3,5-Ethenoporphyrin is a pi -extended porphyrin containing a fused ethene unit between the meso- and beta -positions, exhibiting unique contribution of macrocyclic antiaromaticity. We have recently reported that its analogue, etheno-fused diporphyrin, underwent thermal [2 + 2] cycloaddition to furnish X-shaped cyclobutane-linked tetraporphyrins. Here we demonstrate that the cyclobutane-ring formation is dynamically redox-active. Namely, the tetraporphyrin underwent two-step four-electron oxidation to afford two etheno-fused diporphyrin dications. The reduction of the resulting dication regenerated the cyclobutane-linked tetraporphyrin. The dication was sufficiently stable to allow its isolation under ambient conditions. The structure of the dication has been confirmed by H-1 NMR spectroscopy and X-ray diffraction analysis. Importantly, the simultaneous double C-C bond cleavage in the cyclopropane ring in the tetraporphyrin is exceptional among dynamic redox (dyrex) systems to achieve large structural changes, thus offering new insights for the design of novel redox-active functional organic materials for electrochromic dyes, organic batteries, and organic memories.

DOI： 10.1039/d1sc00438g

Web of Science

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

[16]Norcorrole is an antiaromatic ring-contracted porphyrinoid. Here, we show that the phosphorus insertion of the free-base [16]norcorrole switches its antiaromaticity to aromaticity. The treatment of a free-base meso-dimesityl[16]norcorrole with phosphorus tribromide in pyridine afforded an [18]norcorrole P(V) complex, which exhibited porphyrin-like absorption and fluorescence spectra. The phosphorus center adopted a distorted tetragonal pyramidal coordination geometry. The distinct aromatic nature of the [18]-norcorrole P(V) complex was corroborated both experimentally and theoretically.

DOI： 10.1021/acs.orglett.1c00823

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Replacement of the meso methine carbon atoms of porphyrins with heteroatoms is a powerful strategy for tuning their optical and electronic properties. In particular, 5-oxaporphyrin is an attractive target due to its importance as an intermediate in heme catabolism. In this work, we describe the synthesis and properties of a free-base 5-oxaporphyrinium cation, which was prepared by the ring-closure of a bilindione with trifluoromethanesulfonic anhydride. This free-base 5-oxaporphyrinium cation exhibits dual fluorescence originating from its unique NH tautomerism. In contrast to normal porphyrins, the cis form of the 5-oxaporphyrinium cation is more stable than the trans form due to the effective delocalization of its positive charge. We thus demonstrate here that meso-modified heteroporphyrins enable the manipulation of NH tautomerism in porphyrinic macrocycles.

DOI： 10.1002/anie.202013542

Web of Science

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

meso-Dimethylnorcorrole Ni-II complex exhibited enough stability under ambient conditions despite the distinct antiaromaticity. The small methyl substituents realized a dense and long-range p-stacking in its solid state, which resulted in the superior electron-transporting ability to previously reported Ni-II norcorroles.

DOI： 10.1039/d0dt03143g

Web of Science

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

The synthesis and properties of a 2-to-2 ' 18-to-18 ' doubly linked Ni(ii) norcorrole dimer are described. It adopts a highly planar structure, resulting in effective electronic interactions between the constituent norcorrole units. Nevertheless, each norcorrole unit exhibits substantial antiaromaticity, which stands in sharp contrast to stacked norcorrole dimers.

DOI： 10.1039/d0cc02543g

Web of Science

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

Norcorrole is a ring-contracted porphyrinoid, exhibiting distinct antiaromaticity. Herein, we report the reactions of meso-dimesitylnorcorrole Ni(II) complex with two types of carbenes: dichlorocarbene and an N-heterocyclic carbene (NHC). The reaction with in-situ-generated dichlorocarbene resulted in the double insertion of two chloromethine units to provide a mixture of 5,15-dichloroporphyrin and chlorinated isopyricorroles. The nucleophilic NHC attacked the 3-position of the norcorrole core and the subsequent proton transfer furnished a nonconjugated macrocycle incorporating a diazafulvene segment.

DOI： 10.1021/acs.orglett.0c01402

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1142/S108842461950069X

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Oxidation of 5,15-dithiaporphyrin with meta-chloroperbenzoic acid afforded the corresponding S,S-tetraoxide in good yield. The resultant 5,5,15,15-tetraoxo-5,15-dithiaporphyrin exhibited the highly electron-deficient nature as elucidated by the electrochemical analysis and theoretical calculations. Treatment of tetraoxodithiaporphyrin with zinc(II) acetate and nickel(II) acetate provided the corresponding metal complexes efficiently. Owing to its enhanced Lewis acidity of the metal center by the electron-deficient ligand, the nickel complex underwent facile axial ligation to form pentacoordinate and hexacoordinate high-spin (S=1) complexes in solution and solid, respectively. The binding constant of pyridine to the Ni-II center was significantly higher than those of conventional porphyrin Ni-II complexes. Temperature-dependent magnetic susceptibility measurements of the high-spin Ni-II complex revealed the presence of weak ferromagnetic interactions.

DOI： 10.1002/chem.201903639

Web of Science

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

Hydroxyisooxophlorin is an oxidatively degraded porphyrin that contains one carbonyl carbon, one hydroxymethylene group, and two sp(2)-methine groups at its meso positions. Here we report that oxidation of a free-base meso-hydroxyporphyrin with [bis(trifluoroacetoxy)iodo]benzene in the presence of H2O afforded two regioisomers of hydroxyisooxophlorins, 10-hydroxy-10-iso-5-oxophlorin and 15-hydroxy-15-iso-5-oxophlorin, as major and minor products, respectively. We also examined the reaction mechanism, acid-mediated isomerization, metal complexation behavior, and physical properties of these molecules.

DOI： 10.1021/acs.orglett.9b01066

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

The synthesis of antiaromatic Ni-II-norcorroles having primary, secondary, and tertiary alkyl groups at the reactive meso-positions was attempted. Reductive coupling of a Ni-II-dipyrrin precursor provided Ni-II-meso-dihexylnorcorrole, which underwent substantial degradation on silica gel. Introduction of tert-butyl groups was unsuccessful due to the difficult preparation of the corresponding dipyrrin precursor. Meanwhile, Ni-II-norcorroles with isopropyl and cyclohexyl groups were isolated as stable molecules under ambient conditions. Furthermore, we found that oxidation of Ni-II-meso-dialkylnorcorroles with hydrogen peroxide in the presence of sodium carbonate gave Ni-II-5-oxaporphyrins(2.0.1.0). In contrast, oxidation of Ni-II-meso-dimesitylnorcorrole under the same reaction conditions gave 10-oxaporphyrin(1.1.1.0). The contrasting reactivity can be attributed to the steric congestion around the meso-positions.

DOI： 10.1002/chem.201901292

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.5059/yukigoseikyokaishi.77.512

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41598-018-28311-2

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

Diarylamine-fused subporphyrins 1 a and 1 b were synthesized from β,β-diiodo-meso-chloro subporphyrin 2 through a one-pot procedure involving nucleophilic aromatic substitution and SRN1-type intramolecular fusion reaction as the first example of meso-nitrogen-embedded subporphyrin. While non-fused counterparts 3 b and 4 b display effective fluorescence quenching due to twisted intramolecular charge transfer (TICT) in CH2Cl2 at room temperature, 1 b emits fluorescence with ΦF=0.18 under the same conditions, because conformational twisting is not allowed due to the fused structure. In addition, the oxidative titration with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave cation radical 7 for 1 a and cation radical and dication for 1 b. Actually, cation radical 7 was isolated through separation over silica gel column but was found to slowly decompose in concentrated solutions.

DOI： 10.1002/chem.201801576

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley-VCH Verlag  

Control of open-shell character of meso-meso linked porphyrin meso-oxy radical dimers has been demonstrated by core metalation. Namely, NiII-porphyrin dimer 6Ni exhibits a clear 1H NMR spectrum and a distorted but rather coplanar quinonoidal structure consisting of two ruffled porphyrin rings, in accordance with the previous report. Freebase dimer 6H2 shows a similar quinonoidal structure in the solid state but displays slightly broader and temperature-dependent 1H NMR spectra, indicating a partial diradical character in solution that increases at high temperature. In sharp contrast, bis-imidazole-coordinated ZnII-porphyrin dimer 6ZnIm2 exhibits a perpendicular structure consisting of two planar ZnII-porphyrins and has been characterized as a distinct open-shell diradical on the basis of its non-observable 1H NMR signals, a clear ESR signal, and a characteristic absorption spectrum reaching about 1700 nm. Despite the distinct diradical character, 6ZnIm2 is an extremely stable molecule.

DOI： 10.1002/chem.201705769

Web of Science

Scopus

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

A meso-meso - - triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of -to- doubly Pt-II-bridged subporphyrin dimer 9. Dimer 6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time-resolved transient absorption spectroscopy. X-ray diffraction analysis reveals that 6 has a bowl-shaped structure with a positive Gaussian curvature. Despite the curved structure, 6 exhibits a remarkably red-shifted absorption band at 942nm and a small electrochemical HOMO-LUMO gap (1.35eV), indicating an effectively conjugated -electronic network.

DOI： 10.1002/anie.201707123

Web of Science

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Diphenylphosphine-oxide-fused Ni-II porphyrin 8 was synthesized from 3,5,7-trichloroporphyrin 5 via a reaction sequence of nucleophilic aromatic substitution with lithium diphenylphosphide, oxidation with H2O2, and palladium-catalyzed intramolecular cyclization. Reduction of 8 with HSiCl3 gave diphenylphosphine-fused Ni-II porphyrin 9. The embedded P=O and P moieties serve as a strong electron-accepting and electron-donating group to perturb the optical and electrochemical properties of the Ni-II porphyrin. Ni-II porphyrin 9 is diamagnetic with a low-spin Ni-II center in solution but becomes paramagnetic with a five-coordinated Ni-II center with high-spin (S=1) state in the solid state. Diphenylphosphine-oxide-fused Zn-II porphyrin 10 was also synthesized and shown to form a face-to-face dimer with mutual O-Zn bonds in the crystal and in nonpolar and moderately polar solvents. The dimerization of 10 in CDCl3 has been revealed to be an entropy-driven process with a large entropy gain (S-D=207JK(-1)mol(-1)).

DOI： 10.1002/chem.201700909

Web of Science

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

A new class of aromatic metamorphosis has been developed in which dibenzofurans were converted into triphenylenes. This transformation is composed of three successive operations: (1) nickel-catalyzed ring-opening C-O bond arylation with arylmagnesium bromides, (2) trifluoromethanesulfonylation (triflation) of the resulting hydroxy moiety with Tf2O, and (3) palladium-catalyzed or photoinduced ring closure. In the last ring-closing step, the photoinduced process has proven to be more productive than the palladium-catalyzed one. By employing pi-extended dinaphthofuran as the substrate, dorsally benzo-fused [5]helicene was obtained in a satisfactory yield.

DOI： 10.1021/acs.orglett.6b03861

Web of Science

記述言語：英語  

DOI： 10.1002/chem.201901292

Web of Science

記述言語：英語  

Web of Science

記述言語：日本語  

J-GLOBAL

DOI： 10.1038/s41598-018-28311-2

Web of Science

DOI： 10.1246/bcsj.20180103

Web of Science

DOI： 10.1002/chem.201801576

Web of Science

DOI： 10.1002/anie.201802494

Web of Science

DOI： 10.1002/chem.201705769

Web of Science

DOI： 10.1039/c7dt02815f

Web of Science

DOI： 10.1002/anie.201707123

Web of Science

DOI： 10.1021/jacs.7b05332

Web of Science

DOI： 10.1039/c7qo00093f

Web of Science

DOI： 10.1002/chem.201700909

Web of Science

DOI： 10.1021/acs.orglett.6b03861

Web of Science

DOI： 10.1039/c6sc02721k

Web of Science

DOI： 10.1002/chem.201604301

Web of Science

DOI： 10.1002/anie.201606293

Web of Science

DOI： 10.1039/c5sc04748j

Web of Science

DOI： 10.1002/anie.201501149

Web of Science

DOI： 10.3987/COM-14-S(K)15

Web of Science

DOI： 10.1002/anie.201400632

Web of Science

DOI： 10.1039/c4cc00126e

Web of Science

DOI： 10.1002/ajoc.201300162

Web of Science

DOI： 10.1002/anie.201304794

Web of Science

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