A Novel Hemiporphyrazine Comprising Three Isoindolediimine and Three Thiadiazole Units

Kobayashi, Nagao; Inagaki, Sayaka; Nemykin, Victor N.; Nonomura, Taro

doi:10.1002/1521-3757(20010716)113:14<2782::aid-ange2782>3.0.co;2-n

Cited by 7 publications

(2 citation statements)

References 10 publications

(11 reference statements)

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“…In the case of the N -alkylated triazolehemiporphyrazine ( 1a ), a weak absorption band with a pronounced vibronic progression was seen in the visible region. This weak absorption band was also seen in other triazolehemiporphyrazines. ,, The spectral feature in the short wavelength region of triazolehemiporphyrazines seems to be similar to that of 3 + 3 type expanded hemiporphyrazines, but such a weak absorption band is not seen in the expanded system. , The MCD intensity corresponding to the visible band was almost zero. Complex MCD signals were observed for the relatively intense absorption band in the 350–400 nm region.…”

Section: Resultsmentioning

confidence: 59%

“…5,28,33 The spectral feature in the short wavelength region of triazolehemiporphyrazines seems to be similar to that of 3 + 3 type expanded hemiporphyrazines, but such a weak absorption band is not seen in the expanded system. 10,44 The MCD intensity corresponding to the visible band was almost zero. Complex MCD signals were observed for the relatively intense absorption band in the 350−400 nm region.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

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Unraveling the Electronic Structure of Azolehemiporphyrazines: Direct Spectroscopic Observation of Magnetic Dipole Allowed Nature of the Lowest π–π* Transition of 20π-Electron Porphyrinoids

et al. 2014

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Hemiporphyrazines are a large family of phthalocyanine analogues in which two isoindoline units are replaced by other rings. Here we report unambiguous identification of 20π-electron structure of triazolehemiporphyrazines (1, 2) and thiazolehemiporphyrazine (3) by means of X-ray analysis, various spectroscopic methods, and density functional theory (DFT) calculations. The hemiporphyrazines were compared in detail with dibenzotetraazaporphyrin (4), a structurally related 18π-electron molecule. X-ray analysis revealed that tetrakis(2,6-dimethylphenyloxy)triazolehemiporphyrazine (1b) adopted planar geometry in the solid state. A weak absorption band with a pronounced vibronic progression, observed for all the hemiporphyrazines, was attributed to the lowest π-π* transition with the electric-dipole-forbidden nature. In the case of intrinsically chiral vanadyl triazolehemiporphyrazine (2), a large dissymmetry (g) factor was detected for the CD signal corresponding to the lowest π-π* transition with the magnetic-dipole-allowed nature. Molecular orbital analysis and NICS calculations showed that the azolehemiporphyrazines have a 20π-electron system with a weak paratropic ring current.

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Section: Resultsmentioning

confidence: 59%

Section: ■ Results and Discussionmentioning

confidence: 97%

Unraveling the Electronic Structure of Azolehemiporphyrazines: Direct Spectroscopic Observation of Magnetic Dipole Allowed Nature of the Lowest π–π* Transition of 20π-Electron Porphyrinoids

et al. 2014

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Design and Synthesis of Low HOMO–LUMO Gap N‐Phenylcarbazole‐Substituted Diketopyrrolopyrroles

et al. 2016

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The use of the electron-withdrawing cyano group to lower energy levels and extend light absorption of compounds for optoelectronic applications is well known.T he use of cyano group incorporation has been reported to improve the electron mobility in organic photovoltaics to increase performance. Recently,w eh ave reported that materials based on multiple acceptors including 1,1,4,4-tetracyanobutadiene (TCBD) and diketopyrrolopyrrole (DPP) possesses excellent photophysical characteristics such as strong light absorption,c o-planar structure and good photochemical stability,w hich can be utilized as non-fullerene electron acceptors for bulk heterojunction organics olar cells. To examine the effect of TCBD on the optical properties of DPPs, we designed and synthesized ethyne-bridged N-phenylcarbazole-substituted DPPs and their TCBDd erivatives by Pd-catalyzed Sonogashira cross-couplinga nd [2+ +2] cycloaddition-retroelectrocyclization reactions, respectively.T he photophysical, thermal, electrochemical and computational properties of these compounds were investigated, which show substantial donor-acceptor interactions between the N-phenylcarbazole and DPP moieties. The N-phenylcarbazole-substituted DPPs exhibit excellent thermal stability. The TCBD derivatives showed redshifted, broad charge-transfer bands in the visible region with low HOMO-LUMO gaps compared to the corresponding ethyne-bridged N-phenylcarbazole-substituted compounds. The electrochemical study revealed additional reduction waves in the TCBD-bridged compounds, which correspond to the TCBD moiety itself. Scheme1.Synthesis of N-phenylcarbazole-substituted DPPs 5 and 6.Scheme2.Synthesis of N-phenylcarbazole-substituted TCBDderivatives 7 and 8.

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Synthesechemie expandierter Porphyrine

2003

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Expandierte Porphyrine sind synthetische Analoga der Porphyrine und unterscheiden sich von diesen und anderen natürlichen makrocyclischen Tetrapyrrolen durch einen größeren zentralen Ring mit mindestens 17 Atomen, wobei die ausgedehnte Konjugation erhalten bleibt, die die biologischen Pigmente kennzeichnet. Durch die Erweiterung des zentralen Rings entstehen Verbindungen mit neuen spektralen und elektronischen Merkmalen, ungewöhnlichen Komplexbildungseigenschaften und in vielen Fällen der Eigenschaft, in bestimmten Protonierungszuständen Anionen zu binden. Zum Interesse an den expandierten Porphyrinen trägt auch ihre Schlüsselrolle bei der Klärung von Fragen zur Aromatizität bei. In vielen Fällen weisen sie in der Chemie der Porphyrine einmalige Strukturmerkmale auf, z. B. die nichtplanaren Figure‐Eight‐Konformationen. Dieser Aufsatz beschreibt schwerpunktmäßig die heute verwendeten Syntheseverfahren für expandierte Porphyrine und geht daneben auf spezielle Anwendungsaspekte ein.

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A Novel Hemiporphyrazine Comprising Three Isoindolediimine and Three Thiadiazole Units

Cited by 7 publications

References 10 publications

Unraveling the Electronic Structure of Azolehemiporphyrazines: Direct Spectroscopic Observation of Magnetic Dipole Allowed Nature of the Lowest π–π* Transition of 20π-Electron Porphyrinoids

Unraveling the Electronic Structure of Azolehemiporphyrazines: Direct Spectroscopic Observation of Magnetic Dipole Allowed Nature of the Lowest π–π* Transition of 20π-Electron Porphyrinoids

Design and Synthesis of Low HOMO–LUMO Gap N‐Phenylcarbazole‐Substituted Diketopyrrolopyrroles

Synthesechemie expandierter Porphyrine

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