Recent advances in the synthesis of diazaporphyrins and their chalcogen derivatives

Matano, Yoshihiro

doi:10.1039/d3ob00274h

Cited by 4 publications

(2 citation statements)

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“…Given the absence of other template atoms in their reported synthesis, the atomic radius of boron is likely to fit well into the cavity of the tripyrrolic ring system compared with other metal ions such as Zn 2+ , Cu 2+ , and Ni 2+ , which are frequently used as templates for porphyrin and phthalocyanine synthesis. 40–42 In the first synthesis of boron( iii )-subphthalocyanine ( 1 ), Meller and Ossko used haloboranes, such as BCl 3 , both as a template and as an acid to activate phthalonitrile (Scheme 1). 30 Although the synthetic approach appeared to be applicable to subporphyrins, they have remained undiscoverable for more than 30 years.…”

Section: Synthetic Approachesmentioning

confidence: 99%

“…Given the absence of other template atoms in their reported synthesis, the atomic radius of boron is likely to t well into the cavity of the tripyrrolic ring system compared with other metal ions such as Zn 2+ , Cu 2+ , and Ni 2+ , which are frequently used as templates for porphyrin and phthalocyanine synthesis. [40][41][42] In the rst synthesis of boron(III)-subphthalocyanine (1), Meller and Ossko Fig. 1 Canonical porphyrin and calix [4]pyrrole accessible by acidcatalyzed pyrrole monomer condensation and their contracted analogues, subporphyrin (also known as triphyrin(1.1.1)) and calix [3] pyrrole.…”

Section: Boron-templated Synthesismentioning

confidence: 99%

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Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects

Watanabe,

Pati,

Inokuma

2024

Chem. Sci.

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Section: Synthetic Approachesmentioning

confidence: 99%

Section: Boron-templated Synthesismentioning

confidence: 99%

Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects

Watanabe,

Pati,

Inokuma

2024

Chem. Sci.

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Two Approaches to the Synthesis of Redox‐Switchable 5,10,20‐Triaryl‐5,15‐diazaporphyrinoids

Murata,

Sudoh,

Furukawa

et al. 2024

Chemistry An Asian Journal

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Despite the significant development and extensive application of phthalocyanine and related azaporphyrins, little attention has been paid to meso‐N‐substituted azaporphyrinoids. Here, we report new derivatives of 5,10,20‐triaryl‐5,15‐diazaporphyrinoids (Ar3DAP), which are reversibly redox‐switchable between the 18π‐ and 19π‐electron state. Four kinds of metal(II) complexes and free bases of Ar3DAP were prepared by metal‐templated cyclization of metal(II) complexes of 5,10,15‐triaryl‐10‐azabiladiene‐ac with sodium azide or copper‐catalyzed N‐phenylation of 10,20‐diaryl‐5,15‐diazaporphyrins (Ar2DAP) with diphenyliodonium hexafluorophosphate. In particular, regioselective N‐phenylation of covalently linked Ar2DAP dimer afforded two kinds of dimers bearing one or two meso‐N‐phenyl groups. Cyclic voltammetry revealed that attaching one aryl group onto the meso‐nitrogen atom markedly changed the redox potentials of the DAP ring. The aromaticity and optical properties of the new Ar3DAP π‐electron systems were assessed using various spectroscopic measurements and density functional theory calculations. The distribution pattern of an electron spin in the neutral Ar2DAP–Ar3DAP radical revealed that the meso‐N‐phenyl group had a remarkable effect on spin delocalization of DAP π‐radical. The present study provides valuable information for understanding the effects of the number of meso‐N‐substituents on azaporphyrin‐based π‐electron systems.

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Synthesis, Structure, and Redox and Optical Properties of 5,10,15,20‐Tetraaryl‐5‐azaporphyrinium Salts

Kudoh

Suzuki

Ochiai

et al. 2023

Chemistry A European J

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The fundamental properties of azaporphyrins can be modulated over a wide range by changing the number of meso‐nitrogen atoms. We report herein the first examples of 5,10,15,20‐tetraaryl‐5‐azaporphyrinium (MTAMAP) salts, which were prepared via metal‐templated cyclization of the corresponding zinc(II) and copper(II) complexes of 10‐aryl‐1‐chloro‐19‐benzoyl‐5,15‐dimesityl‐10‐azabiladiene‐ac. The inclusion of one meso‐nitrogen atom in the 5,10,15,20‐tetraarylporphyrin skeleton considerably changes the redox and optical properties as well as the degree of aromaticity of the porphyrin ring. The present findings suggest that MTAMAP salts would be promising scaffolds for the development of new azaporphyrin‐based ionic fluorophores and photosensitizers.

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Recent advances in the synthesis of diazaporphyrins and their chalcogen derivatives

Abstract: Porphyrins are highly influential functional materials in the field of science owing to their fascinating colors and diverse electrochemical and optical properties. Peripheral modification of porphyrin rings with nitrogen is...

Cited by 4 publications

References 81 publications

Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects

Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects

Two Approaches to the Synthesis of Redox‐Switchable 5,10,20‐Triaryl‐5,15‐diazaporphyrinoids

Synthesis, Structure, and Redox and Optical Properties of 5,10,15,20‐Tetraaryl‐5‐azaporphyrinium Salts

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