Country：Japan

Country：Japan

Country：Japan

Country：Japan

Country：Japan

Country：Japan

Country：Japan

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

DOI： 10.1021/jacs.4c07985

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A Ni(ii) diazaporphyrin with carboxy groups afforded a stable HOF through intermolecular hydrogen-bonding interactions, which exhibited high semiconductivity as well as stability toward heating and various solvents.

DOI： 10.1039/d4sc03455d

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Other Link： https://doi.org/10.1039/D4SC03455D

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DOI： 10.3762/bjoc.20.172

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DOI： 10.1021/jacs.4c07091

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Abstract

Recently, π–π stacked antiaromatic π‐systems have received considerable attention because they can exhibit stacked‐ring aromaticity due to substantial intermolecular orbital interactions. Here, we report three antiaromatic norcorrole dimers that self‐assemble to form supramolecular architectures through chiral self‐sorting. A 2,2’‐linked norcorrole dimer with 3,5‐di‐tert‐butylphenyl groups forms a π‐stacked dimer both in solid and solution states via homochiral self‐sorting. Its association constant in solution is (3.6±1.7)×10⁵ M⁻¹ at 20 °C. In the solid state, 3,3’‐linked norcorrole dimers with 3,5‐di‐tert‐butylphenyl and phenyl groups afford macrocyclic and helical supramolecular assemblies via heterochiral and homochiral self‐sorting, respectively. Notably, the subtle modification in the substituent resulted in a complete change in the structure of the aggregates and the chiral self‐sorting mode. The present findings demonstrate that structural manipulation in antiaromatic monomer units leads to the formation of various supramolecular assemblies on the basis of the attractive interactions between antiaromatic π‐systems.

DOI： 10.1002/chem.202400292

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Alkyne cycloisomerization of 2,7,10,15-tetra(ortho-alkynylphenyl)benzo[g,p]chrysene containing bulky 4-alkoxy-2,6-dimethylphenyl groups at the alkyne terminals selectively proceeded at the sterically crowded bay-region.

DOI： 10.1039/d4cc01573h

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DOI： 10.1021/jacs.4c05358

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Norcorroles with 3,4,5-trialkoxyphenyl moieties were synthesized to form thermotropic liquid crystals (LCs), in which triple-decker stacking structures were formed. The LC state exhibited discotic columnar structures to exhibit high electric conductivity.

DOI： 10.1039/d4sc01633e

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The diatropic (red) and paratropic (yellow) current density of the antiaromatic Ni(ii) bis(pentafluorophenyl)norcorrole and of its aromatic face-to-face stacked dimer.

DOI： 10.1039/d4cp00968a

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Norcorrole Ni(II) complexes have recently received considerable attention as readily accessible antiaromatic molecules. Their high stabil-ity under ambient conditions and easy synthesis have enabled the exploration of the intrinsic properties of antiaromatic molecules. Here, we report the synthesis and properties of directly meso−meso singly-linked porphyrin−norcorrole hybrids and triply-linked porphy-rin−norcorrole hybrids. The singly-linked and triply-linked porphyrin−norcorrole hybrids were fully characterized, including their X-ray structural analysis. Because of their orthogonal conformation, singly-linked hybrids maintained the individual electronic property of por-phyrin and norcorrole subunits The triply-linked hybrid showed a significant decrease in the HOMO–LUMO gaps, the paratropic ring current in the norcorrole subunit, and the diamagnetic ring current in the porphyrin subunit. Furthermore, the triply-linked hybrid exhib-ited singlet diradical characteristics, confirmed by VT-NMR, ESR, and SQUID experiments.

DOI： 10.1002/anie.202401233

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DOI： 10.1021/jacs.4c01142

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The interaction force was measured as the adhesive force acting between norcorrole molecules anchored to the probe surface and the sample surface. This study reveals substantial interactions in π-stacked antiaromatics at the single-molecule scale.

DOI： 10.1039/d3tc04166b

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DOI： 10.1021/acs.jpclett.3c03337

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Oxford University Press (OUP)  

Abstract

Here, we disclose the effect of substitution at the bay-region of 9,9′-bifluorenylidene on its optical and electrochemical properties. Bay-brominated 9,9′-bifluorenylidene was synthesized by the reductive dimerization of 4,5-dibromofluorenone with triethyl phosphite. The subsequent Suzuki–Miyaura cross-coupling afforded arylated derivatives. X-ray diffraction analysis revealed that the bulky bay-substituents twist the overall structure through the relay of the steric repulsion from the bay-region to the fjord-region. The π-extension at the bay-region with tolyl and 4-dimethylaminophenyl groups increases the electron-donating ability, while the introduction of bromo groups enhances the electron-accepting ability.

DOI： 10.1093/chemle/upad015

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Other Link： https://academic.oup.com/chemlett/article-pdf/53/1/upad015/56961460/upad015.pdf

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

DOI： 10.1021/acs.orglett.3c04323

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DOI： 10.1021/jacs.3c10250

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DOI： 10.1021/acs.orglett.3c03428

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DOI： 10.1039/d3qo01661g

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DOI： 10.1021/acs.jpclett.3c02260

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DOI： 10.1016/j.cplett.2023.140641

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DOI： 10.1002/anie.202300437

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DOI： 10.1002/chem.202300249

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DOI： 10.1021/acs.orglett.2c04173

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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

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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

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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

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DOI： 10.1021/jacs.2c08795

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DOI： 10.1016/j.xcrp.2022.101045

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DOI： 10.1039/d2ob01410f

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DOI： 10.1002/ejoc.202200770

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Post-functionalization of porphyrinoid catalysts provides a powerful tool for fine-tuning their electronic structure. We have succeeded in the stepwise methylation of the peripheral nitrogen atoms in ruthenium and cobalt 5,15-diazaporphyrins. The axial coordination of an anion to the metal center accelerates the second methylation through charge neutralization. N-Methylation of the diazaporphyrin complexes effectively controls their electron deficiency, Lewis acidity, and catalytic activity.

DOI： 10.1002/asia.202200305

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DOI： 10.1002/asia.202200244

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DOI： 10.1039/d2cp00295g

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<p>Ring closure of 1-oxo-19-(phenylamino)bilin affords 5-azaporphyrinium cations. The introduction of a phenyl group on the <i>meso</i>-nitrogen induces a positive charge in the porphyrinic skeleton. Steric repulsion between the <i>N</i>-phenyl and <i>β</i>-ethyl substituents results in the deformation of the inner-cavity to a rectangle. The rectangular cavity and cationic charge induced the unique tautomerization of the inner-NH protons.</p>

DOI： 10.1246/cl.220122

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DOI： 10.1039/d2cc00522k

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DOI： 10.1246/bcsj.20220026

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<p>Dibenzo[<i>h</i>,<i>t</i>]rubicene was synthesized from 1,5-dichloroanthraquinone via an internally dimethoxylated intermediate. In contrast to the planar conformation of rubicene, dibenzo[<i>h</i>,<i>t</i>]rubicene adopted a double-helicene-like structure due to the intramolecular steric repulsion around the fused benzene-rings. Theoretical calculation suggests that the helical inversion occurs frequently with an inversion barrier of 4.8 kcal mol⁻¹. The HOMO–LUMO gap of dibenzo[<i>h</i>,<i>t</i>]rubicene is smaller than that of rubicene, resulting in its red-shifted absorption tailing to 690 nm.</p>

DOI： 10.1246/cl.210754

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<p>The synthesis of Pd(II) and Cu(II) 10-azacorroles with a <i>meso</i>-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.</p>

DOI： 10.1246/cl.210777

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DOI： 10.1002/anie.202112456

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<p>A radical anion of Ni(II) <i>meso</i>-dimesitylnorcorrole was prepared and isolated upon chemical reduction of the corresponding neutral species with cobaltocene (Co^IICp₂). The radical anion was substantially stable under degassed solution conditions. X-ray crystal analysis of the radical anion revealed that the structural change by one-electron reduction is marginal. DFT calculations demonstrated that the reorganization energy of Ni(II) norcorrole upon one-electron reduction is smaller than those of Zn(II) porphyrin and C₆₀ fullerenes.</p>

DOI： 10.1246/cl.210715

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DOI： 10.1002/anie.202114230

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We report the synthesis and properties of indeno[1,2,3,4-pqra]perylene, which was prepared by the fusion of one anthracene unit with one naphthalene unit via three carbon-carbon bonds. The synthetic route through two-fold C−H arylation enabled not only the synthesis of unsubstituted indenoperylene, but also rapid access to its arylated derivatives on the gram scale. Indenoperylene is a medium-sized aromatic hydrocarbon with the composition C24H12 that is isomeric to coronene. Nevertheless, its absorption covers the entire visible region owing to its small HOMO-LUMO gap. Furthermore, indenoperylene exhibits high stability despite the absence of peripheral substituents. We propose that the unique electronic structure of indenoperylene originates from the coexistence of an electron-withdrawing subunit (benzoaceanthrylene) and an electron-donating subunit (perylene). The electronic properties of indenoperylene were modulated via post-functionalization through regioselective bromination. The current research demonstrates that indenoperylene is a promising candidate as a main skeleton for near-infrared-responsive and redox-active materials.

DOI： 10.1002/chem.202103647

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DOI： 10.1002/batt.202100193

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<jats:p> Fluorination of sp<jats:sup>3</jats:sup> C–H bonds has attracted considerable attention as a promising method for the synthesis of organofluorine compounds. Manganese porphyrins have been extensively investigated as catalysts in the fluorination of saturated sp<jats:sup>3</jats:sup> C–H bonds. Recently, we have found that iron(III) 5,15-diazaporphyrins, which are porphyrin analogues with imine-type sp<jats:sup>2</jats:sup>-hybridized nitrogen atoms at the meso-positions, showed high catalytic performance in the oxidation of sp<jats:sup>3</jats:sup> C–H bonds. Here we disclose the synthesis, structure, and electronic properties of manganese(III) 5,15-diazaporphyrins. We also demonstrate the catalysis of chloromanganese(III) 5,15-diazaporphyrins for benzylic fluorination. </jats:p>

DOI： 10.1142/S1088424621500887

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DOI： 10.1002/anie.202109003

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DOI： 10.1055/a-1437-9917

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DOI： 10.1021/jacs.1c04348

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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

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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

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DOI： 10.1002/anie.202103667

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DOI： 10.1002/chem.202100454

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DOI： 10.1039/d1dt00893e

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<p>A series of nickel(II) pyridinophane complexes were synthesized and characterized by X-ray crystallographic analysis. Their IR spectra supported the existence of mononuclear nickel(II) complexes in solution. Furthermore, we conducted catalytic C–H oxidation of cyclooctane with nickel(II) pyridinophanes as the catalysts. The activity of nickel(II) pyridinophanes was affected by steric hindrance around the nitrogen atoms.</p>

DOI： 10.1246/cl.210074

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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

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[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

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DOI： 10.1002/chem.202005077

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DOI： 10.1021/acs.orglett.1c00253

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DOI： 10.1002/ajoc.202000722

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DOI： 10.1002/anie.202013542

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DOI： 10.1039/d0cc07804b

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<p>Dual-ion Na–organic batteries were provided with anti-aromatic NiNc, exposing inherent charge–discharge behavior with high discharge capacity, high durability, and high Coulombic efficiency with high-density currents.</p>

DOI： 10.1039/D1MA00007A

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DOI： 10.1039/d0cc06495e

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DOI： 10.1002/asia.202001129

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DOI： 10.1039/d0dt02727h

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DOI： 10.1039/d0dt03143g

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DOI： 10.1021/acs.inorgchem.0c02166

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DOI： 10.1038/s41467-020-17684-6

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DOI： 10.1021/jacs.0c04096

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DOI： 10.1002/chem.202002053

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DOI： 10.1039/d0cc02543g

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：公益社団法人 日本化学会  

<p>反芳香族化合物は不安定な化合物であるが，それを上下に接近させて重ねると芳香族化合物になり，安定化することが分かってきた。これまで，芳香族性の起源は二次元的なπ電子の広がりであると考えられてきた。しかし最新の研究により，2つの分子の間の三次元的なπ電子の広がりによっても芳香族性が生じることが示された。また，反芳香族化合物が芳香族化合物よりも互いに接近しやすいことも分かってきた。分子が近づいて電荷が移動しやすくなるため，有機半導体などへの応用が期待される。</p>

DOI： 10.20665/kakyoshi.68.6_268

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DOI： 10.1021/acs.orglett.0c01402

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DOI： 10.1246/cl.200083

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DOI： 10.1142/S108842461950069X

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DOI： 10.1002/chem.201905402

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N‐Alkylation significantly changes the electronic and optical properties, as well as the reactivity of nitrogen‐containing π‐conjugated molecules. In this study, it is found that treating 5,15‐diazaporphyrins with methyl triflate selectively affords the corresponding N ‐methyl‐5,15‐diazaporphyrinium cations in good yield. N‐Methylation substantially alters the electronic properties and reactivity of diazaporphyrins. The electron‐accepting properties of the N ‐methyl‐5,15‐diazaporphyrinium cations are enhanced due to their lowered LUMO level. Stabilization of the LUMO energy enables regio‐ and stereoselective Diels–Alder reactions of the cationic diazaporphyrin with cyclopentadiene. N‐Methylation also enhances the acidity of the inner NH protons, and thus, allows facile deprotonation to provide nitrogen‐substituted isoporphyrin analogues with only one NH group in the central cavity.

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DOI： 10.1021/acs.joc.9b01655

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DOI： 10.1021/jacs.9b09556

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DOI： 10.1021/acs.orglett.9b03699

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DOI： 10.1002/chem.201903639

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DOI： 10.1246/cl.190369

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DOI： 10.1002/chem.201902123

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DOI： 10.1038/s41467-019-11467-4

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DOI： 10.3390/molecules24132433

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DOI： 10.1039/c8cc07489e

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DOI： 10.1002/cphc.201800745

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DOI： 10.1021/jacs.8b04673

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DOI： 10.1021/jacs.8b00798

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DOI： 10.1039/c7qm00593h

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DOI： 10.1002/anie.201712961

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DOI： 10.1039/c7sc04453d

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DOI： 10.1021/acs.orglett.7b03764

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DOI： 10.1016/j.jinorgbio.2017.10.012

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<p>Recently, π-conjugated molecules with curved-π surface have attracted considerable interest for their unique properties originating from their curved structures. However, most of them consist of only carbon and hydrogen atoms. In these situations, we have developed novel synthetic protocols for construction of distorted structures directly from 2D π-conjugated molecules under mild reaction conditions. By applying phenol and aniline oxidation methods, we have succeeded in the synthesis of highly distorted cyclophanes, π-extended heterohelicenes, and highly twisted porphyrin oligomers. Furthermore, we have succeeded in the synthesis of a nitrogen-embedded buckybowl as a novel bowl-shaped π-conjugated molecule with a pyrrolic nitrogen in its skeleton. These heteroatom containing curved-π conjugated molecules exhibit unique characteristics due to the combination of the curved structure with heteroatoms such as circularly polarized luminescence, strong C₆₀ binding, and near IR electrochromism. We believe that the chemistry of heteroatom containing curved-π conjugated molecules would enhance the potential of three-dimensional π-conjugated molecules for molecular materials.</p>

DOI： 10.5059/YUKIGOSEIKYOKAISHI.76.37

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DOI： 10.1002/anie.201707212

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DOI： 10.1021/acs.joc.7b01899

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DOI： 10.1002/anie.201706134

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DOI： 10.1021/acs.orglett.7b02390

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DOI： 10.1002/asia.201700840

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DOI： 10.1038/ncomms15984

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DOI： 10.1246/cl.170363

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DOI： 10.1039/c7tc01270e

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Oxidation of dicyanomethyl-substituted hexa-peri-hexabenzocoronenes (HBCs) furnished a tetracyanoethylene-bridged HBC dimer and trimer. The solid state structures of the oligomers were elucidated using single crystal X-ray diffraction analysis. In the solution state, these HBC oligomers exhibited conformational isomerism, depending on solvents and temperatures. Moreover, solid samples of the HBC dimer and trimer exhibited mechanochromism, showing near IR absorption upon grinding through generation of radical species. The formed radical was stable for 4 months, indicating the persistent nature of the radical species. These NIR mechanochromic behaviours of the HBC oligomers were originated from the reversible C–C bond dissociation and formation of a tetracyanoethylene linkage between the HBC units.

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DOI： 10.1002/chem.201701474

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10-Silacorroles were obtained from the Pd-catalyzed silylative cyclization of a bis(α,α′-dibromodipyrrin) Ni^II precursor with dihydrosilanes. These 10-silacorroles show substantially red-shifted absorption bands relative to those of normal porphyrins and isocorroles. Notably, the corresponding free base and Zn^II 10-silacorroles exhibit emissions in the NIR region. Theoretical calculations on these 10-silacorroles revealed the presence of σ*–π* conjugation between the silyl group and the tetrapyrrole π system, which significantly lowers their LUMO energy levels.

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DOI： 10.1002/chem.201700729

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DOI： 10.1021/acs.orglett.7b01074

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DOI： 10.1021/acs.chemrev.6b00427

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DOI： 10.1039/c6cc09444a

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DOI： 10.1038/ncomms13620

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DOI： 10.1002/anie.201607237

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DOI： 10.1142/9789813149571_0003

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DOI： 10.1002/chem.201601306

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A novel synthetic protocol has been developed for free-base 10-azacorroles. Ni(0)-mediated homocoupling of nitrogen-bridged bisdipyrrin Zn(II) complexes afforded a series of free-base 5,15-diaryl-10-azacorroles in good yields. Pd(II) and Cu(II) complexes have been prepared through metalation of free-base 10-azacorroles. Optical and electrochemical properties of 10-azacorrole metal complexes can be tuned by meso-aryl substituents and central metals. Cyclic voltammetry and theoretical calculations elucidated that the central metals of 10-azacorroles significantly affected their electronic properties.

DOI： 10.1021/acs.orglett.6b01323

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Pyrenyl-substituted 1,3-butadienes bearing alkyl and aryl groups have been synthesized by palladium-catalyzed addition of 2-borylpyrene to internal alkynes. On UV irradiation, 1-pyrenylbutadienes undergo photochromism in solution. In the solid state, 1-pyrenyl-1,2,3,4-tetraaryl-1,3-butadiene exhibits red-shifted and broad emission as compared with the alkylated butadiene. The charge-carrier mobility of 1-pyrenyl-1,2,3,4-tetraalkyl-1,3-butadiene is higher than that of the arylated butadiene.

DOI： 10.1246/cl.151181

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DOI： 10.1002/asia.201600105

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DOI： 10.1002/chem.201600066

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Japan Society of Applied Physics  

DOI： 10.11470/jsapmeeting.2016.1.0_3881

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DOI： 10.1039/c5cc10247b

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DOI： 10.1039/c6cc02918c

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Dehydrative coupling between indoles and isatins provided indolylindolinones in good yields as novel dyes with wide-range absorption due to intramolecular charge-transfer interactions. The HOMO and LUMO levels of indolylindolinones could be manipulated individually by the introduction of substituents on the indole and isatin units, respectively. Indolylindolinones served as a bidentate ligand to Ni(II) and Cu(II) ions to provide stable metal complexes. Metal coordination induced large bathochromic shift of the lowest-energy absorption band to the near-infrared region.

DOI： 10.1246/cl.150815

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We have established the facile and efficient protocol to synthesize distorted 71-conjugated molecules. Oxidation of amino-substituted porphyrins proceeded with high regioselectivity to produce pyrazine fused dimers. X-ray diffraction analysis revealed its highly twisted structure. Electrochemical and optical measurements indicated the twisting mostly influences on HOMO. The sequential use of our protocol has achieved the synthesis of unidirectionally twisted porphyrin tetramers efficiently. NMR analysis suggested that the racemization barrier of twisting increases on oligomerization. To the best of our knowledge, this is the first observation of a similar phenomenon observed in polymer science for twisted, jt-conjugated molecules. The present findings represent an important advance towards the long-term goal of preparing -conjugated molecular wires, whose properties can be fine-tuned through molecular twisting.

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DOI： 10.1002/anie.201505130

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Curved π-conjugated molecules have attracted considerable interest because of the unique properties originating from their curved π surface. However, the synthesis of such distorted molecules requires harsh conditions, which hamper easy access to heteroatom-containing curved π systems. Here we report the synthesis of a π-extended azacorannulene with nitrogen in its centre. The oxidation of 9-aminophenanthrene provides tetrabenzocarbazole, which is converted to the azabuckybowl through palladium-catalysed intramolecular coupling. The electron-donating nature and curved π surface of the azabuckybowl enable its tight association with C[60] in solution and solid states. High charge mobility is observed for the azabuckybowl/C[60] assembly. This compound may be of interest in the fields of curved π systems as fullerene hosts, anisotropic π donors and precursors to nitrogen-containing nanocarbon materials.

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DOI： 10.1038/ncomms9215

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DOI： 10.1002/anie.201502666

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DOI： 10.1021/ja511905f

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DOI： 10.3987/COM-14-S(K)15

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Authorship：Lead author,　Last author,　Corresponding author   Language：English   Publishing type：Part of collection (book)   Publisher：Springer Japan  

Most syntheses of meso-substituted porphyrinoid rely on acid-catalyzed condensation of pyrrole segments with aldehyde units followed by oxidation. This standard procedure is convenient but generally is low yielding. However, modern synthetic methodologies would offer an expeditious route to several intriguing porphyrinoids. In particular, the metal template strategy using dipyrrin metal complexes is effective to construct porphyrin-like cyclic π-conjugated systems, which are otherwise difficult to access by the conventional methodology.

DOI： 10.1007/978-4-431-55357-1_14

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DOI： 10.1039/c5cc06921a

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DOI： 10.1142/S108842461450093X

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DOI： 10.1039/c5cc00764j

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DOI： 10.1002/anie.201408852

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Halogenation and phenylthiolation of hexabenzocoronenetetraone were performed. We found that introduction of substituents at the fjord regions induced substantial curvature of the hexabenzocoronene (HBC) plane through steric repulsion between the substituents and proximal hydrogen atoms. This method allows construction of curved HBC derivatives, which would allow formation of novel supramolecular structures.

DOI： 10.1246/cl.140577

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Treatment of bis(trimethylsilylethynyl)porphyrin with strong acids afforded doubly oxoethano-fused porphyrin with perfect regioselectivity. The oxoethano-fused porphyrin was more electron deficient than <i>meso</i>-acetylporphyrin because of the coplanar orientation of the carbonyl groups to the porphyrin π system.

DOI： 10.1246/cl.140470

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We have developed a facile procedure for the synthesis of π-extended fluorubins from perylene bisimides. Iridium-catalyzed direct borylation, the Suzuki–Miyaura cross-coupling, and an acid-condensation sequence afforded π-extended fluorubins <b>1</b> in moderate yields. X-ray diffraction analysis revealed a planar structure of <b>1</b>. In addition, optical analysis and DFT calculations indicated the presence of intramolecular charge-transfer interactions in <b>1c</b>.

DOI： 10.1246/cl.140330

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DOI： 10.1021/ol501131j

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A set of hybrids having gradual variation in distances between hexaphyrin and bodipy moieties, given by uses of phenylene, biphenylene, and triphenyelene bridges was prepared. Efficient PET processes from bodipy (donor) to [26]- or [28]hexaphyrin (acceptor) were successfully observed, where the PET speed was controlled by intramolecular distances between the donor and the acceptor. UV irradiation at 515nm raised a band corresponding to the bodipy absorption. As the time delayed, the bodipy bands decreased and new absorption bands at 615 and 580nm corresponding to respective absorption bands of [28]- and [26]-hybrids gradually appeared. Whereas the femtosecond transient absorption spectra of [28]/[26]-hybrids having terphenylene bridges completely showed energy transfers from bodipy to hexaphyrin, irradiation of the hybrids using 615 and 580nm pulses did not induce opposite ways of the PET process. On the basis of enlarged center-to-center-distances of [26]-hybrids than those of [28]-hybrids, the set of [26]-hybrids resulted in slow decay/rise processes. PET parameters obtained with the experiments were fairly consistent with the PET parameters calculated.

DOI： 10.1002/chem.201400315

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DOI： 10.1021/ol500569b

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DOI： 10.1002/anie.201310374

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Society of Synthetic Organic Chemistry, Japan  

Porphyrin is a representative functional molecule, which consists of four pyrrole units linked by four carbon atoms with an 18π aromatic character. Most of porphyrin syntheses rely on acid-catalyzed condensation of pyrrole with aldehydes followed by oxidation, which are low-yielding in many cases. To establish more effective porphyrin synthesis, we have devoted our effort to combine porphyrin chemistry and modern organic synthesis through transition metal-mediated reactions. In this article, we focus on synthesis of novel porphyrin analogues through coupling of dipyrrin precursors. The metal-templated strategy using dipyrrin metal complexes was found to be quite efficient to construct porphyrin-like cyclic π-conjugated systems consisting of the dipyrrin unit, which exhibit intriguing optical and electronic properties.

DOI： 10.5059/yukigoseikyokaishi.72.149

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：東京 : 有機合成化学協会  

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DOI： 10.1002/ange.201309921

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Japan Academy  

Borylated functional π-systems are useful building blocks to enable efficient synthesis of novel molecular architectures with beautiful structures, intriguing properties and unique functions. Introduction of boronic ester substituents to a variety of extended π-systems can be achieved through either iridium-catalyzed direct C–H borylation or the two-step procedure via electrophilic halogenation followed by palladium-catalyzed borylation. This review article focuses on our recent progress on borylation of large π-conjugated systems such as porphyrins, perylene bisimides, hexabenzocoronenes and dipyrrins.

DOI： 10.2183/pjab.90.1

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DOI： 10.1039/c3cc48738e

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DOI： 10.1142/S1088424614500412

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DOI： 10.1002/anie.201306905

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A shapely figure: A [32]octaphyrin(1.0.1.0.1.0.1.0) bis[palladium(II)] complex was selectively obtained through a metal-templated intermolecular homocoupling of a α,α'-dibromodipyrrin palladium(II) complex without formation the norcorrole. The weak antiaromatic character of the figure-eight [32]octaphyrin(1.0.1.0.1.0.1.0) system has been elucidated by spectroscopic measurements and DFT calculations.

DOI： 10.1002/ange.201306905

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Pyridine-fused perylene tetracarboxylic acid bisimides (PBIs) were synthesized via Suzuki-Miyaura coupling and acid condensation. The fused PBIs with electron-donating substituents exhibited an intramolecular charge transfer Interaction. One of the N-alkyl substituents was selectively removed with BBr3 to create an amidine guest binding site. A hydrogen bonding Interaction with pentafluorobenzoic acid changed the absorption spectra and enhanced fluorescence.

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DOI： 10.1002/ajoc.201300033

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We have demonstrated that the iridium-catalyzed direct borylation of hexa-peri-hexabenzocoronene (HBC) enables regioselective introduction of boryl groups to the para-, ortho-, and meta-substituted HBCs in high yields. The boryl groups have been transformed into various functionalities such as hydroxy, cyano, ethynyl, and amino groups. We have elucidated that the substituents significantly influence the photophysical properties of HBCs to enhance fluorescence quantum yields. DFT calculations revealed that the origin of the substituent effect is the lift in degeneracy in the frontier orbitals by an interaction with electron-donating and electron-withdrawing substituents at the para- and ortho-positions. The change in molecular orbitals results in an increase of the transition probability from the S-0 -&gt; S-1 states. In addition, the two-photon absorption cross-section values of para-substituted HBCs are significantly larger than those of ortho-and meta-substituted HBCs.

DOI： 10.1002/asia.201200723

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A strained relationship: Oxidation of dihydroxy-substituted acenes provides face-to-face [2.2]metacyclophane-like dimers (see scheme
Ored, Si of iPr 3Si groupsblue). The products exhibited highly distorted structures caused by steric repulsion. UV/Vis and electrochemical analysis revealed that the HOMO-LUMO gap was decreased upon dimerization. Copyright © 2013 WILEY-VCH Verlag GmbH &amp
Co. KGaA, Weinheim.

DOI： 10.1002/anie.201301180

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Treatment of meso-mesityl 5,15-diazaporphyrin with alkyllithiums in toluene at low temperature provided monoalkylated diazachlorins through highly regioselective nucleophilic addition at the β-position near the meso-nitrogen atom. © The Royal Society of Chemistry 2013.

DOI： 10.1039/c3cc41907j

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A linear arrangement of BODIPY dimers and trimers was transformed into boron-bridged box, ladder and cage structures on treatment with spacer units possessing multiple diol moieties.

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Facile synthesis of meso-aryl-substituted 5,15-dithiaporphyrins and 10-thiacorroles has been achieved by sulfidation of a,a'-dichlorodipyrrin metal complexes with sodium sulfide in DMF. Thiacorrole metal complexes exhibit distinct aromaticity due to 18?p-conjugation including the lone pair on sulfur, whereas dithiaporphyrins are nonaromatic judging from 1H NMR spectra, X-ray analysis, and absorption spectra. We have found that NiII and AlIII dithiaporphyrin complexes undergo smooth thermal sulfur extrusion reaction to give the corresponding thiacorrole complexes, whereas free base, ZnII, PdII, and PtII dithiaporphyrin complexes did not exhibit the similar reactivity. The DFT calculations have elucidated a reaction pathway involving an episulfide intermediate, which can explain the markedly different reactivity among dithiaporphyrin metal complexes.

DOI： 10.1002/chem.201203255

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Direct C-H borylation of hexa-peri-hexabenzocoronenes (HBCs) has been achieved under iridium catalysis, which allows efficient synthesis of hydroxy-substituted HBCs by oxidation of the boryl groups. Further oxidation of dihydroxy HBC with phenyliodine bis(trifluoroacetate) (PIFA) afforded tetraoxo-substituted HBC without any regioisomers, which can be considered as a pi-extended quinone.

DOI： 10.1021/ol300743f

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Synthesis of nickel(II) complexes of meso-aryl-substituted azacorroles was performed by BuchwaldHartwig amination of a dipyrrin NiII complex with benzylamine through C?N and C?C coupling. The highly planar structure of NiII azacorroles was elucidated by X-ray diffraction analysis. 1H NMR analysis and nucleus independent chemical shift (NICS) calculation on NiII azacorrole revealed its distinct aromaticity with [17]triaza-annulene 18p conjugation. In addition, acylation of azacorrole selectively afforded N- and C-acylated azacorroles depending on the reaction conditions, showing the dual reactivity of azacorroles.

DOI： 10.1002/chem.201200485

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

Energy and electron transfer from frameworks of nanoporous or mesostructured materials to guest species in the nanochannels have been attracting much attention because of their increasing availability for the design and construction of solid photofunctional systems, such as luminescent materials, photovoltaic devices, and photocatalysts. In the present study, energy and electron-transfer behavior of dye-doped periodic mesostructured organosilica films with different host-guest arrangements were systematically examined. Fluorescent tetraphenylpyrene (TPPy)-silica mesostructured films were used as a host donor. The location of guest perylene bisimide (PBI) dye molecules, acting as an acceptor, could be controlled on the basis of the molecular design of the PBI substituent groups. PBI dyes with bulky substituents and polar anchoring groups were located at the pore surface with low self-aggregation, which induced efficient energy or electron transfer because of the close host-guest arrangement. However, PBI dye with bulky and hydrophobic substituents was located in the center of template surfactant micelles; the fluorescence emission from the host TPPy groups was hardly quenched when the host-guest distance was longer than the critical Forster radius (ca. 4.5 nm). The relationship between the energy or electron-transfer efficiency and the location of guest species in the channels of mesostructured organosilica was first revealed by molecular design of the PBI substituents.

DOI： 10.1021/la204645k

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A biphenyl-fused BODIPY was synthesized through a facile oxidative cyclization of peripheral aryl-substituents at the beta-position of the BODIPY unit. The extended pi-system of the fused BODIPY induces near-infrared (NIR) absorption and strong pi-pi interactions in the solid state. These features are beneficial for the application of the dye as a functional material. The biphenyl-fused BODIPY dye was demonstrated to exhibit photocurrent conversion ability on the basis of its n-type semiconducting property.

DOI： 10.1021/ol2033916

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1,3-Phenylene-bridged perylenebisimide dimer (PBI2) and trimer (PBI3) were prepared along with monomer reference (PBI1) using perylene imide-anhydride 5 as a key precursor. 3,3-Dimethylbut-1-ylsubstituents were introduced at the 2,5-positions of perylenebisimide (PBI) to improve the solubilities of PBI oligomers. Actually, no serious aggregation of PBI2 and PBI3 was detected in their dilute CH2Cl2 solutions. Under these conditions, intramolecular electronic interactions among PBI chromophores have been revealed by measuring the photophysical properties at their ensemble and single-molecule levels. The excitation energy transfer times of PBI2 (0.16 ps) and PBI3 (0.60 ps) were determined from the two different observables, anisotropy depolarization, and singlet-singlet annihilation, respectively, which are considered as the incoherent Forster-type energy hopping (EEH) times as compared with the EEH time constant (1.97 ps) calculated on the basis of the Forster mechanism. The relatively short EEH times compared to similar PBI oligomers can be attributed to 1,3-phenylene linker, which assures a short distance between the chromophores and, as a consequence, makes it hard to treat the PBI unit as a point dipole. The limitation of point-dipole approximation to describe the PBI oligomers and additional through-bond type interactions can be attributed as the causes of the discrepancies in excitation energy transfer times. Considering these photophysical properties, we can suggest that 1,3-phenylene-linked PBI oligomers have potentials as molecular photonic devices including the artificial light-harvesting system.

DOI： 10.1021/jp208855u

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

A cyclic indole tetramer has been synthesized via an iridium-catalysed C-H borylation-cross coupling sequence. The tetraindole has a highly distorted structure, but can be oxidized with bromine and water into a highly planar macrocycle. The oxidized macrocycle can capture metal ions in its inner cavity as a novel porphyrin analogue, accompanied by a significant colour change from purple to blue or black.

DOI： 10.1039/c1sc00665g

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

DOI： 10.1002/anie.201105394

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DOI： 10.1002/anie.201109091

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DOI： 10.1002/anie.201108037

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DOI： 10.1002/anie.201204863

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DOI： 10.1002/anie.201204395

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The direct arylation on the thienyl groups of a diarylethene with various aryl iodides efficiently provided arylated dithienylethenes under palladium catalysis. Unsymmetrically substituted dithienylethenes were also synthesized by this protocol. This procedure allows a rapid access to a variety of aryl-substituted dithienylethenes from a single substrate of a simple dithienylethene.

DOI： 10.1021/ol2026069

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

A meso-to-beta directly linked hexameric porphyrin triangle was synthesized by the Suzuki-Miyaura cross-coupling reaction via either one-pot or a stepwise route. Hexakis-zine(II) complex of the porphyrin triangle exhibits a split Soret band in the absorption spectrum, reflecting the effective exciton coupling over the whole molecule.

DOI： 10.1246/cl.2011.902

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

Pt(II)and Pt(IV)porphyrin pincer complexes were synthesized and characterized. Their structures and electronic properties were influenced by the valence state of platinum at the outer coordination site. The considerable distortion in the porphyrin core of the Pt(II) complex was relieved in the Pt(IV) complex, due to the change of the coordination geometry of platinum. Oxidation of the phenylplatinum(II) pincer complex with iodine induced a facile carbon carbon bond formation reaction at the meso position via reductive elimination.

DOI： 10.1021/om100644n

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

Highly stable eta(2)-porphyrin Ru(II) pi complexes have been synthesized. The formation of the eta(2) pi it bond has been facilitated through pi-pi stacking interactions between the porphyrin and the planar ligand on Ru. pi coordination of ruthenium to porphyrin results in dramatic changes in the aromaticity and electronic properties. These properties are controllable via fine-tuning of the ligand on ruthenium.

DOI： 10.1021/ja104842h

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A meso,meso-diketohexaphyrin was isolated and characterized as a chemically stable non-Kekule singlet biradicaloid. Two unpaired electrons are seemingly delocalized on two tripyrrolic units separated by C=O bonds. These results underscore the potential of expanded porphyrins to achieve unique electronic states.

DOI： 10.1021/ja101040s

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

DOI： 10.1002/anie.200906017

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

Novel meso-meso directly linked porphyrin dinners tethered at beta-pyrrolic positions of the porphyrin ring with 2-propenoic acids or 2,4-pentadienoic acids were prepared for sensitization of nanocrystalline titanium dioxide solar cells. Most importantly, the absorption spectra of dimeric porphyrins were notably extended into the midvisible region in the solar spectrum while the LUMO levels are sufficiently high to inject electrons to the conduction band of TiO2. Among these dimers, PEG-2b-bd-Zn2 dimer, bearing a poly(ethylene glycol) end group at one meso position, showed the highest incident photon-to-photocurrent generation with 47% efficiency at the Soret region as well as the power conversion efficiency of 4.2% under standard AM 1.5 solar condition. To elucidate electronic structures and excited-state properties, UV-vis absorption and emission, cyclic voltammetry measurements, and density functional theory Calculations were performed. To Our best knowledge, the obtained conversion efficiency of 4.2% from PEG-2b-bd-Zn2-sensitized DSSC is the highest photovoltaic performance among DSSCs based on oligomeric porphyrins. Thus, this work suggests that the wide spectral response of directly linked porphyrin dimers due to the excitonic coupling is an intriguing aspect of directly linked pophyrin dimers to be utilized for DSSCs and gives an insight into the design of more efficient light-harvesting molecules.

DOI： 10.1021/jp905675x

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

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

DOI： 10.1021/ol902294r

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DOI： 10.1002/chem.200902143

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

Directly and doubly beta,beta'-linked corrole dimers (DH3CD, DH2CD, and DZnCD) are excellent platforms for the investigation of intercorrole interactions because of their enforced coplanar geometries and short edge-to-edge distances. Through the use of these molecules along with the reference monomer H3CM and the singly beta,beta'-linked corrole dimer SH3CD, the intercorrole interactions have been systematically studied by density functional theory calculations, ultrafast photophysical measurements, and two-photon absorption measurements. A particular focus was placed on revealing factors that are important for the induced photophysical properties of the doubly linked corrole dimers compared with corrole monomer. In the doubly linked corrole dinners, strong molecular orbital interactions caused by the coplanar geometry and the short interchromophoric distance give rise to perturbations of the electronic states that are responsible for the red-shifted and intensified Q-like band in DH3CD and the broad NIR absorption bands and fast excitation-energy relaxation processes in DH2CD and DZnCD. On the other hand, electronic communication between corrole units is prohibited by the structurally constrained octagonal core in the center, so each constituent corrole unit in the doubly linked corrole dimers maintains an intrinsic pi-conjugation system. Consequently, the overall aromaticity of the directly linked corrole dimers can be explained in terms of a linear sum of two constituent corrole monomers, and the singlet biradical character of DH2CD and DZnCD can be understood in terms of two unpaired electrons (one from each constituent oxidized corrole monomer) and their appropriate interaction. In addition, the nonlinear optical properties of DH2CD and DZnCD with singlet biradical character have been confirmed to be significantly enhanced compared with those of closed-shell DH3CD. Collectively, double beta,beta'-linkages of corroles provide the coplanar geometry with a short interchromophoric distance and the strained octagonal core that play key roles in allowing the strong molecular orbital interactions and restricting the electronic communication between the two corroles, respectively.

DOI： 10.1021/ja900220y

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Metalation of [28]hexaphyrin(1.1.1.1.1.1) with [RhCl(CO)(2)](2) resulted in the formation of an antiaromatic bis-Rh(I) complex, which can be oxidized to an aromatic bis-Rh(I) complex with retention of its rectangular structure.

DOI： 10.1039/b905859a

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Iridium-catalyzed direct borylation has been applied to meso-substituted dipyrromethane and boron dipyrrin (BODIPY) dyes. Borylation is highly regioselective and complementary: it occurs exclusively at the alpha position for meso-mesityldipyrromethane and at the beta positions for meso-mesityl BODIPY dye. This regioselective borylation enables a variety of alpha- and beta-substituted BODIPY dyes to be synthesized. Introduction of alpha,beta-enoate and alpha,beta,gamma,delta-dienoate functions into BODIPY dyes at the alpha or beta positions was achieved by rhodium-catalyzed Heck-type addition of the borylated compounds to acrylate and 2,4-pentadienoate esters. This functionalization has a significant effect on the electronic properties of BODIPY dyes, as seen in substantial redshift of the absorption and emission spectra. Comparative studies showed that the alpha- and beta-substituted series of BODIPY dyes show substantially different photophysical properties, and thus the importance of the position to be functionalized is highlighted.

DOI： 10.1002/chem.200802541

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meso-Octakis(pentafluorophenyl)-substituted [36]octaphyrin(1.1.1.1.1.1.1.1) (1) is a figure-of-eight nonaromatic macrocycle that serves its a unique platform to induce a metathesis-like splitting reaction upon bis-Cu(II) metalation. To get a better understanding of this splitting reaction, we examined the metalation of 1 with several metal ions. In contrast with the smooth and quantitative splitting reaction of bis-Cu(II) complex 1-CuCu, free-base 1, mono-Cu(II) complex 1-Cu, and bis-Zi(II) complex 1-ZnZn do not undergo the splitting reaction. Mono-Con complex 1-Co was selectively produced from metalation with the Co(II) ion, from which hybrid complex 1-CoCu was synthesized. The hybrid complex 1-CoCu undergoes the splitting reaction to give 2-Co and 2-Cu quantitatively. Activation parameters of the splitting reactions were determined: E(a) = 104 kJ mol(-1), Delta H double dagger 101 kJ mol(-1), Delta S double dagger = -25.0 J mol(-1) K(-1), and Delta V double dagger = 18 cm(3)mol(-1) for 1-CuCu and E(a) = 105 kJ mol(-1), Delta H double dagger = 102 kJ mol(-1), and Delta S double dagger = -29.9 J mol(-1) K(-1) for 1-CoCu. A marked difference between the splitting reaction reactivity of 1-CuCu and 1-ZnZn has been examined by DFT calculations at the B3LYP/631SDD// B3LYP/LANL2DZ level, which revealed that the reaction proceeds through it stepwise route involving initial C1-C20 bond formation to give INT1 as the rate-determining step and subsequent C21-C40 bond formation to give a spirocyclobutane intermediate (INT2), followed by a radical reverse cycloaddition reaction to give two metalloporphyrins. Inherent instability of 1-CuCu, which may arise from its strongly distorted structure, was indicated to be a main factor in the smooth splitting reaction. Finally, a new bis-Pd(II) complex (5-PdPd) was isolated in the metalation of 1 with Pd(OAc)(2) in a 9:1 mixture of 2,2,2-trifluoroethanol and methanol as a manifestation of the transannular electronic interaction in metalated octaphyrin complexes. Collectively, these results underscore the importance of the transannular electronic interactions that are enhanced by metalation, depending upon the coordinated metal ions.

DOI： 10.1002/chem.200900454

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

meso-meso-Linked diporphyrins fabricated with multiple unsaturated carboxylic acid groups are efficiently synthesized by the use of transition-metal catalysis. Iridium-catalyzed direct borylation of meso-meso-linked diporphyrins furnish multi-borylated diporphyrins with high regioselectivity. Then, the introduction of alpha,beta- or alpha,beta,gamma,delta-unsaturated ester functions to the diporphyrins is achieved through rhodium-catalyzed Heck-type addition of the borylated diporphyrins to acrylate or 2,4-pentadienoate esters. Saponification of the esters to the corresponding acids is accomplished in high yields. The post-modification of diporphyrin 6 smoothly provides a water-soluble multiporphyrin array 1 in 84% total yield in 3 steps. This functionalization significantly affects the electronic properties of the porphyrins, resulting in different energy levels of each porphyrin unit. The absorption and fluorescence spectra indicate efficient energy transfer in the porphyrin dimers.

DOI： 10.1002/asia.200900053

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

Our study focus on beta, beta'-doubly linked corrole dimers (CDs) on mica and Au(1 1 1) surface using samples prepared by the synthetic method described by Osuka group appeared on recent publication [S. Hiroto, K. Furukawa, H. Shinokubo, A. Osuka, J. Am. Chem. Soc. 128 (2006) 12380]. Atomic force microscopy (AFM) and scanning tunneling microscopy (STM) were used to investigate the self-assembled structure of corrole dimers adsorbed on mica and Au(1 1 1) surfaces respectively at room temperature in air. The CDs adopt a dissimilar adsorption modality due to the different surface free energy of the different substrates. These types of molecular layers provide a useful platform for the study of surface and interface phenomena outside a vacuum system. It is potentially useful for practical fabrication of molecular devices because of the simplicity of the sample preparation and the stability of the interface in ambient conditions. (C) 2009 Elsevier B. V. All rights reserved.

DOI： 10.1016/j.apsusc.2009.01.026

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Our study first focus on two types of corrole dimers oxidized and reduced forms on highly oriented pyrolytic graphite (HOPG) surface. Scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and contact angle measurement (CAM) were used to investigate the self-assembled monolayers of corrole dimers adsorbed on HOPG surfaces at room temperature in air. XPS and CAM results have confirmed both two molecules adsorbed on an HOPG surface and formed self-assembled films, and STM experiments found that the corrole dimers adsorbed on HOPG surfaces form similar lobes. The different stable space structure of the oxidized form molecule (OFM) and reduced form molecule (RFM), led to the diversity of the tetramer structural dimensions. The occurrence of molecular aggregations and assembly was controlled by the interactions between molecular-molecular and molecule-substrate. The electrostatic interactions between the molecules control the geometrical sizes and molecule-substrate interactions determine topographical shapes of the self-assembled corrole dimers on HOPG surface. Copyright (C) 2009 John Wiley & Sons, Ltd.

DOI： 10.1002/sia.3011

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DOI： 10.1002/anie.200805674

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DMF-appended cyclometalated platinum(II) and -(IV) porphyrins were synthesized via the double cleavage of sp(2) C-H and sp(3) C-H bonds on one platinum center.

DOI： 10.1021/ic8019149

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：GEORG THIEME VERLAG KG  

The reaction of meso-bromoporphyrins with norbornene-fused porphyrins afforded novel norbornane-bridged diporphyrins in excellent yields via palladium-catalyzed [3+2] annulation reaction.

DOI： 10.1055/s-0028-1083267

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The development of porphyrin synthesis by means of transition metal-catalyzed reactions is explored in this feature article. Porphyrins have been receiving much attention in a wide area of chemistry as functional dyes, non-linear optical materials, ligands for a variety of metals, structural motifs in supramolecules, and so forth. However, they have been merely recognized as a reaction substrate in transition metal-catalyzed transformations. Recently, application of such new methodologies to porphyrin synthesis has proven to be very powerful to create new types of porphyrinic compounds, which have their own intriguing structures and properties. New transformations on porphyrins via transition metal catalysis offer us prospects of new designs of architectures, thus facilitating further development of this important class of functional molecules.

DOI： 10.1039/b817941g

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The treatment of 3,5-dibenzoylporphyrins with ammonium acetate provided novel oxopyridochlorins as the first examples of pyridine-fused porphyrinoids, which displayed absorption bands reaching into the near IR region and an ability to sensitize singlet oxygen effectively.

DOI： 10.1039/b819284g

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Authorship：Corresponding author   Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：The Society of Physical Organic Chemistry, Japan  

In most of cases the linkage of cyclic porphyrin arrays have been limited to phenylene- or ethynylene-bridges. Here we report the synthesis of novel cyclic porphyrin arrays including 2,2-bithiophene as a <I>meso</I>-to-<I>meso</I> spacer unit. The ¹H-NMR spectra displayed the almost same chemical shifts for these cyclic porphyrin arrays except the slight shifts of thiophene proton, indicating high symmetric cyclic structure of them in solution. On the other hand, the X-ray diffraction analysis revealed the solid-state structure of cyclic 3mer Zn(II) complex which showed, to our surprise, the asymmetric conformation in which two of the bithiophene units were <I>syn</I> isomer and one of them was <I>anti</I> isomer. This isomerization of spacer units causes the molecule to apparently bend.

DOI： 10.11494/kisoyuki.2009.0.242.0

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Oxidation of 2,18-diborylporphyrin provided 2,18-dihydroxyporphyrin, which shows solvent-dependent keto-enol tautomerism and dimerization through hydrogen bonding interaction in solution. Further oxidation of 2,18-dihydroxyporphyrins afforded doubly and directly linked dioxoisobacteriochlorin face-to-face dimers.

DOI： 10.1021/ja807659h

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A directly Pt(IV)-bridged cofacial diporphyrin has been synthesized by the cyclometalation reaction of beta-pyridylporphyrin with a Pt(IV) salt. Upon treatment with methylhydrazine, the Pt(IV) bridge is reduced to the Pt(II) center, resulting in a Pt(II)-bridged cofacial dimer with a helicity inversion of the complex as well as change in eletronic communication through the metal bridge.

DOI： 10.1021/ja8066385

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meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) have been examined by (1)H, (13)C, and (19)F NMR spectroscopies, UV-vis absorption spectroscopy, magnetic circular dichroism spectroscopy, and single-crystal X-ray diffraction analysis. All of these data consistently indicate that [28]hexaphyrins(1.1.1.1.1.1) in solution at 25 degrees C exist largely as an equilibrium among several rapidly interconverting twisted Mobius conformations with distinct aromaticities, with a small contribution from a planar rectangular conformation with antiaromatic character at slightly higher energy. In the solid state, [28]hexaphyrins(1.1.1.1.1.1) take either planar or Mobius-twisted conformations, depending upon the meso-aryl substituents and crystallization conditions, indicating a small energy difference between the two conformers. Importantly, when the temperature is decreased to -100 degrees C in THF, these rapid interconversions among Mobius conformations are frozen, allowing the detection of a single [28]hexaphyrin(1.1.1.1.1.1) species having a Mobius conformation. Detailed analyses of the solid-state Mobius structures of compounds 2b, 2c, and 2f showed that singly twisted structures are achieved without serious strain and that cyclic pi-conjugation is well-preserved, as needed for exhibiting strong diatropic ring currents. Actually, the harmonic-oscillator model for aromaticity (HOMA) values of these structures are significantly large (0.85, 0.69, and 0.71, respectively), confirming the first demonstration of stable Mobius aromatic systems consisting of free-base expanded porphyrins without the assistance of metal coordination.

DOI： 10.1021/ja801983d

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Functionalized porphyrins at meso- and beta-positions with different carboxylic acid groups were prepared to investigate electronic and photovoltaic properties as dye-sensitized nanocrystalline-TiO2 solar cells. The electronic structures of the porphyrin macrocyclic core are strongly coupled with olefinic side chains so that the absorption spectrum exhibits largely broad and red-shifted Soret and Q-bands, especially up to 475 nm at the Soret band in a porphyrin doubly functionalized with malonic diacid groups. Among porphyrin derivatives prepared in this study, 2b-bdta-Zn exhibits the maximum overall conversion efficiency of 3.03% and the maximum incident photon to current efficiency of 60. 1% in the Soret band region, superior to the others. From such photovoltaic performances, we can suggest that multiple pathways through olefinic side chains at two beta-positions enhance the overall electron injection efficiency and the moderate distance between the porphyrin sensitizer and the TiO2 semiconductor layer is important, retarding the charge recombination processes. As a consequence, these combined effects give rise to higher photovoltaic efficiency in photovoltaic regenerative solar cells.

DOI： 10.1021/jp804258q

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Authorship：Lead author   Language：English   Publishing type：Research paper (scientific journal)  

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

Direct functionalization of aromatic substituents on [28]hexaphyrin was achieved by Ir-catalyzed borylation with the Smith-Miyaura-Hartwig protocol. High para. selectivity was observed in the reaction on 2,6-dichlorophenyl and 2,6-dimethoxyphenyl substituents of [28]hexaphyrin. The reaction with [26]hexaphyrin resulted only in reduction of the substrate to provide [28]hexaphyrin without borylation, thus highlighting the importance of the oxidation state of substrates in this catalytic transformation. The borylated hexaphyrin can be used for Suzuki-Miyaura cross-coupling reaction. (c) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.01.069

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

Direct functionalization of aromatic substituents on [28]hexaphyrin was achieved by iridium-catalyzed borylation with theSmith–Miyaura–Hartwig protocol. High para selectivity was observed in the reaction on 2,6-dichlorophenyl and 2,6-dimethoxyphenylsubstituents of [28]hexaphyrin. The reaction with [26]hexaphyrin resulted only in reduction of the substrate to provide [28]hexaphyrinwithout borylation, thus highlighting the importance of the oxidation state of substrates in this catalytic transformation. The borylatedhexaphyrin can be used for Suzuki–Miyaura cross coupling reaction.

CiNii Research

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

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

DOI： 10.1021/ol7028299

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

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

A facile introduction of alpha,beta-or alpha,beta,gamma,delta-unsaturated ester functions onto porphyrins was achieved through rhodium-catalyzed addition of beta-borylporphyrins to acrylate or 2,4-pentadienoate esters. The reaction of meso-borylporphyrins with acrylates exclusively afforded saturated esters by 1,4-conjugate addition under the same re-mode (Heck-type versus conjugate addition) is highly dependent on the reaction site (beta versus meso). This functionalization has a significant impact on the electronic properties of the pi system of porphyrins, which induces a substantial redshift and broadening in the absorption spectra by effective conjugation through the beta positions. The coplanar structure of the unsaturated ester moieties with respect to the porphyrin core has been unambiguously elucidated by X-ray crystallographic analysis.

DOI： 10.1002/chem.200701943

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

DOI： 10.1002/anie.200704407

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

DOI： 10.1002/anie.200801269