A 1,5‐Naphthyridine‐Fused Porphyrin Dimer: Intense NIR Absorption and Facile Redox Interconversion with Its Reduced Congener

Fujimoto, Keisuke; Osuka, Atsuhiro

doi:10.1002/chem.201800854

Cited by 17 publications

(19 citation statements)

References 67 publications

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“…The HOMO and LUMO levels of 3 are delocalized on the whole p-conjugated skeleton. The HOMO of 2 is in accordance with the LUMO of 3, reflecting the two-electron redox in their p systems [25].…”

Section: Dft Calculationsmentioning

confidence: 57%

A near-infrared benzoquinone-coupled BODIPY: Synthesis, spectroscopic and electrochemical properties

Liu

Jiang

Gai

et al. 2019

J. Porphyrins Phthalocyanines

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A near-infrared absorbing boron-dipyrromethene (BODIPY) chromophore coupled with two benzoquinone moieties at its 3,5-positions, 3, was prepared via Knoevenagel condensation of 1,3,5,7-tetramethyl-8-(4[Formula: see text]-benzonitrile) BODIPY 1 with 3,5-di-tert-butyl-4-hydroxybenzaldehyde to afford 1,7-dimethyl-3,5-di-(4[Formula: see text]-hydroxy-3[Formula: see text],5[Formula: see text]-di-tert-butyl styryl)-8-(4[Formula: see text]-benzonitrile) BODIPY 2, followed by oxidization with Ag2O in good yield (91%). The UV-vis-NIR absorption spectrum of 3 exhibits two major bands at 795 and 895 nm in the near-IR region, while 2shows maximum absorbance at 661 nm and strong fluorescence at 692 nm ([Formula: see text] 0.59). The cyclic voltammetry of 3 consists of two pairs of reversible one-electron reductions at -0.61 V and -0.88 V and two pairs of one-electron oxidation waves at 0.26 V and 0.54 V. Compared with the redox potentials of 2([Formula: see text] V and [Formula: see text] 0.25 V), the first reduction of 3 is anodically shifted for 710 mV, whereas the first oxidation potential is close. Theoretical calculation reveals that conjugation with the benzoquinone moieties on the BODIPY chromophore significantly lowers the LUMO energy level and the HOMO–LUMO energy gap, resulting in a dramatic bathochromic shift of the S0–S1 transition of 3 compared with that of 2. X-ray crystallographic analysis of 3 reveals that the whole molecule adopts a V-type twisted conformation along the delocalized [Formula: see text]-conjugated pathway.

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Section: Dft Calculationsmentioning

confidence: 57%

A near-infrared benzoquinone-coupled BODIPY: Synthesis, spectroscopic and electrochemical properties

Liu

Jiang

Gai

et al. 2019

J. Porphyrins Phthalocyanines

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“…Recently [ 39 ], starting from 2-iodo-5,10,15-tris(3,5-di- tert -butylphenyl)porphyrin niquel(II) complex 95 ( Scheme 25 ), β-to-bethynylene-bridged Ni II porphyrin dimer 96 was obtained by a two-fold Stille coupling reaction with a half equivalent of bis(tributylstannyl)acetylene.…”

Section: Synthesis Of Fused 15-naphthyridinesmentioning

confidence: 99%

“…The dimmer 97 exhibits an intense NIR absorption and narrow HOMO-LUMO gap with a remarkably low reduction potential mainly due to the effective bonding interactions in the LUMO through the 1,4-diazabutadiene linkage. In contrast, the reduced dimmer 98 has high HOMO energy and shows a relative large HOMO-LUMO gap compared to that of 97 [ 39 ].…”

Section: Other Applications Of Fused 15-naphthyridinesmentioning

confidence: 99%

Fused 1,5-Naphthyridines: Synthetic Tools and Applications

et al. 2020

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Heterocyclic nitrogen compounds, including fused 1,5-naphthyridines, have versatile applications in the fields of synthetic organic chemistry and play an important role in the field of medicinal chemistry, as many of them have a wide range of biological activities. In this review, a wide range of synthetic protocols for the construction of this scaffold are presented. For example, Friedländer, Skraup, Semmlere-Wolff, and hetero-Diels-Alder, among others, are well known classical synthetic protocols used for the construction of the main 1,5-naphthyridine scaffold. These syntheses are classified according to the nature of the cycle fused to the 1,5-naphthyridine ring: carbocycles, nitrogen heterocycles, oxygen heterocycles, and sulphur heterocycles. In addition, taking into account the aforementioned versatility of these heterocycles, their reactivity is presented as well as their use as a ligand for metal complexes formation. Finally, those fused 1,5-naphthyridines that present biological activity and optical applications, among others, are indicated.

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“…[24] The oxidative intramolecular fusion of amino substituents has been employed also in porphyrinc hemistry.F or example, Osuka et al reportedt he synthesis of a1 ,5-naphthyridinefused porphyrin dimer 13 (Scheme 8). [25] In their study,o xidation was performed on a b,b'-ethynylene-bridged meso-amino Ni II porphyrin dimer 12 with PbO 2 .Asimilar reaction was conducted for the synthesis of an azepine-fused Ni II porphyrin dimer 15 from ad irectly b-b linked mono-meso-aminosubstituted porphyrin dimer 14 (Scheme 9). [26] Interestingly,t he use of ab is-meso-amino-substituted substrate 16 led to pyrazinef usion along with cleavage of the porphyrin ring (Scheme10).…”

Section: Intramolecular Cànbond Formation To Heteroaromaticsmentioning

confidence: 99%

“…For example, Osuka et al. reported the synthesis of a 1,5‐naphthyridine‐fused porphyrin dimer 13 (Scheme ) . In their study, oxidation was performed on a β,β′‐ethynylene‐bridged meso ‐amino Ni II porphyrin dimer 12 with PbO 2 .…”

Section: Intramolecular Covalent Bond Formation Through the Oxidationmentioning

confidence: 99%

Synthesis of π‐Functional Molecules through Oxidation of Aromatic Amines

Hiroto

2019

Chemistry An Asian Journal

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In this review,w ef ocus on the synthesiso fp-conjugated functional molecules by the oxidation of aromatic amines, which is one of the most effective methods fort he constructiono fC ÀC, CÀN, and NÀNb onds between two pconjugated molecular units,a nd consider their characteristics and applications. Polyanilines are the most common products of the oxidation of aromatic amines;h owever,a zobenzenes, phenazines, and 1,1'-binaphthyl-2,2'-diaminesm ay be produced in this manner also, depending on the reaction conditions. Recent advances in the methodology of aniline oxidation have led to the development of high-regioselectivity industrial-scale syntheses of optically or electroactive pfunctional dyes containing nitrogen atoms. In particular,t he regioselective fusion of p-extended aromatic amines can be used to prepare distorted p-conjugated molecules under mild reactionc onditions, allowing the construction of unprecedented curved nitrogen-containing p-conjugated molecules.Scheme1.Aniline oxidations.Scheme2.Reactionpathways for aniline oxidation.[a] Prof.

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A 1,5‐Naphthyridine‐Fused Porphyrin Dimer: Intense NIR Absorption and Facile Redox Interconversion with Its Reduced Congener

Cited by 17 publications

References 67 publications

A near-infrared benzoquinone-coupled BODIPY: Synthesis, spectroscopic and electrochemical properties

A near-infrared benzoquinone-coupled BODIPY: Synthesis, spectroscopic and electrochemical properties

Fused 1,5-Naphthyridines: Synthetic Tools and Applications

Synthesis of π‐Functional Molecules through Oxidation of Aromatic Amines

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