Norihito Fukui

Creating cool fusion: The oxidative fusion of meso-(diarylamino)porphyrins depends heavily on the structures of the diarylamino groups. Bridged diarylamino groups result in the oxidative fusion of 3,5-di-tert-butylphenyl groups to the porphyrin moiety (blue), while non-bridged diarylamino groups invoke formation of nitrogen-embedded aminophenylene-fused porphyrins (red). As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials

Porphyrin tapes possessing meso-meso β-β β-β triple direct linkages have been targets of extensive studies because of their fully conjugated characteristic π-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 β-β linkage(s) of the porphyrin tapes. The carbonyl-inserted porphyrin arch-tapes were efficiently synthesized by double fusion reactions of β-to-β carbonyl-bridged porphyrin oligomers w

Oxidative fusion reactions of <i>meso</i>-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 °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

Establishing design principles to create nonplanar π-conjugated molecules is crucial for the development of novel functional materials. Herein, we describe the synthesis and properties of dinaphtho[1,8-bc:1′,8′-ef]azepine bisimides (DNABIs). Their molecular design is conceptually based on the insertion of a nitrogen atom into a perylene bisimide core. We have synthesized several DNABI derivatives with a hydrogen atom, a primary alkyl group, or an aryl group on the central nitrogen atom. These DN

The synthesis and properties of dinaphtho[1,8-<i>bc</i>:1',8'-<i>ef</i>]thiepine bisimide (DNTBI) and its oxides are described. Their molecular design is conceptually based on the insertion of a sulfur atom into the perylene bisimide (PBI) core. These sulfur-inserted PBI derivatives adopt nonplanar structures, which significantly increases their solubility in common organic solvents. Upon electron injection, light irradiation, or heating, DNTBI and its sulfoxides undergo sulfur extrusion reactio

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

The chlorination of β-halo or β,β-dihaloporphyrins with 2-chloro-1,3-bis(methoxycarbonyl)guanidine (Palau'Chlor) proceeded selectively at the neighboring unsubstituted meso position to afford meso,β-dihalo or meso,β,β-trihaloporphyrins. Such oligohaloporphyrins are useful platforms for constructing more-elaborate porphyrin-based extended π systems. For example, meso-chloro-β,β-diiodoporphyrin participated in an efficient single-step synthesis of a diphenylamine-fused porphyrin. In addition, meso

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

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/π interaction. The late-stage cyanation of the dimer tuned its AIE color from green to orange.

Oxidation of 10,15,20-triaryl Ni(ii)-porphyrins bearing an electron-withdrawing substituent at the 5-position with DDQ and FeCl₃ gave 10,12- and 18,20-doubly phenylene-fused Ni(ii)-porphyrins regioselectively. A doubly phenylene-fused <i>meso</i>-chloro porphyrin thus prepared was reductively coupled to give a <i>meso</i>-<i>meso</i> linked dimer, which was further converted to a quadruply phenylene-fused <i>meso</i>-<i>meso</i>, β-β, β-β triply linked Zn(ii)-diporphyrin <i>via</i> in

Der Modus der oxidative Anellierung von Meso(diarylamino)porphyrinen hängt stark von der Struktur der Diarylaminogruppen ab. Verbrückte Diarylaminogruppen führen zur Anellierung von 3,5-Di-tert-butylphenyl-Ringen an den Porphyrinkern (blau), nichtverbrückte Diarylaminogruppen ergeben Aminophenylen-anellierte Porphyrine mit Brückenkopf-N-Atomen (rot).

Singly and doubly 1,2-phenylene-inserted Ni^II porphyrin arch-tape dimers 3 and 9 were synthesized from the corresponding β-to-β 1,2-phenylene-bridged Ni^II 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 fus

Figure-eight-shaped nonplanar π-systems adopt distinctive chiral <i>D</i>₂-symmetric structures, which are ideal for realizing efficient circularly polarized luminescence (CPL). However, the short-step and enantioselective synthesis of figure-eight π-systems represents a considerable challenge for the conventional bottom-up synthetic strategy. Herein, we report that the oxidative cleavage of the internal double bond of a commercially available polycyclic aromatic hydrocarbon, i.e., di

Abstract The chlorination of β‐halo or β,β‐dihaloporphyrins with 2‐chloro‐1,3‐bis(methoxycarbonyl)guanidine (Palau′Chlor) proceeded selectively at the neighboring unsubstituted meso position to afford meso,β‐dihalo or meso,β,β‐trihaloporphyrins. Such oligohaloporphyrins are useful platforms for constructing more‐elaborate porphyrin‐based extended π systems. For example, meso‐chloro‐β,β‐diiodoporphyrin participated in an efficient single‐step synthesis of a diphenylamine‐fused porphyrin. In addit

7,8-Dehydropurpurin has attracted much attention owing to the dual 18π- and 20π-electron circuits in its macrocyclic conjugation. The two-fold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne furnished 7,8-dehydropurpurin dimers. The 8(a) ,8(a) -linked dimer displays a red-shifted and enhanced absorption band in the NIR region and a small electrochemical HOMO-LUMO band gap as a consequence of efficient conjugation between the two coplanar 7,8-dehydropurpurin units.