Carbaporphyrin Dimers That Bear a Rigid Naphthalene Motif as an Internal Strap

Hong, Jung-Ho; Aslam, Adil S.; Cho, Beomhee; Ko, Min-Sung; Kim, Young-Hoon; Heo, Jungseok; Cho, Dong-Gyu

doi:10.1021/acs.orglett.1c00252

Cited by 17 publications

(23 citation statements)

References 34 publications

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“…For each macrocycle, the corresponding palladium complex, 370.3b or 370.4b , was obtained under standard conditions. Naphthalene-containing analogues 370.5a , b and the bismacrocyclic systems 370.7a were obtained in a similar way. In each case, the corresponding palladium(II) complex could be obtained.…”

Section: Macrocyclic Systemsmentioning

confidence: 65%

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

et al. 2021

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Section: Macrocyclic Systemsmentioning

confidence: 65%

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

et al. 2021

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“…1 H NMR spectra are referenced to tetramethylsilane as an internal standard or the residual solvent signal of the respective solvent: CDCl 3 : δ = 7.26 ppm. 13 C NMR spectra are referenced to the following signals: CDCl 3 : δ = 77.26 ppm. The following abbreviations for multiplicities were used: singlet (s), broad singlet (br), doublet (d), triplet (t), quartet (q), multiplet (m), and combinations thereof, i.e., doublet of doublets (dd).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis, Structure, and Optical Properties of a Bis-Macrocycle Derived from a Highly Emissive 1,3,6,8-Tetra(1H-pyrrol-2-yl)pyrene

et al. 2022

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A tetra-functionalized pyrene precursor 4b is prepared using the Suzuki–Miyaura coupling of 1,3,6,8-tetrabromopyrene with N-Boc-2-pyrroleboronic acid. 4b displayed a blue emission with a high quantum yield (ϕF = 0.89). 4b is subjected to [3 + 2] Lewis acid-catalyzed condensation with 2,2′-bithiophene-dialcohol 5, affording a planar bis-N 2 S 2 internally linked with pyrene. The single-crystal X-ray structure of bis-N 2 S 2 revealed a planar conformation with all of the pyrrolic nitrogens and thiophenic sulfurs pointing toward the macrocyclic core. Further, the reduction of bis-N 2 S 2 was attempted in the presence of Zn/NH4Cl at room temperature in CHCl3. A sharp color change from pink to brown was observed presumably due to the formation of its reduced congener bis-N 2 S 2 –2H. However, the reduced species was found to revert back to its oxidized form over a period of 25 min in CHCl3. Density functional theory (DFT) studies reveal that the two monocyclic halves of bis-N 2 S 2 –2H exhibit differences in aromaticity depending on amino and imino pyrroles present inside each individual core. Such a conversion was also monitored by ultraviolet–visible (UV–vis) absorption spectral studies, and the exact composition of bis-N 2 S 2 –2H was confirmed by High-resolution/mass spectrometry (HR/MS) analysis. Experimental and theoretical studies reveal a weak aromatic character of bis-N 2 S 2 due to the absence of global conjugation.

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“…The studies indicated that fluorenophyrin was a nonaromatic distorted macrocycle and the fluorene moiety was in completely out-of-plane arrangement with the rest of the macrocycle. In continuation of our studies on fluorene-embedded porphyrinoids, herein we report the synthesis of bis-(fluorene)-embedded hexaphyrins 2a/2b , which are expanded porphyrins − containing two fluorene moieties and four pyrrole rings connected via six meso carbons in a macrocyclic framework. These hexaphyrins 2a/2b were investigated by high-resolution mass spectrometry (HRMS), nuclear magnetic resonance (NMR), absorption, electrochemical, and density functional theory (DFT)/time-dependent (TD)-DFT studies, and we present our findings herein.…”

Section: Introductionmentioning

confidence: 99%

Bis-(Fluorene)-Embedded Hexaphyrins

Yadav

Ravikanth

2022

J. Org. Chem.

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The polyaromatic hydrocarbon containing expanded porphyrins, bis-(fluorene)-embedded hexaphyrins, were synthesized by condensing fluorene-based tripyrrane with pentafluorobenzaldehyde in CH2Cl2 in the presence of 1 equiv of BF3·OEt2 under an inert atmosphere followed by oxidation with DDQ in open air at room temperature. The reaction worked only when 1 equiv of BF3·OEt2 was added to the reaction mixture under concentrated reaction conditions. The bis-(fluorene)-embedded macrocycles were characterized and studied by high-resolution mass spectrometry (HRMS), nuclear magnetic resonance (NMR), absorption, electrochemical, and density functional theory (DFT)/time-dependent (TD)-DFT techniques. In 1H NMR, the hexaphyrins showed a few broad unresolved resonances at room temperature, but the NMR spectra were well-resolved at lower temperatures, indicating that the hexaphyrins were very flexible. The DFT-optimized structures indicated that the two fluorene units at the crossing point of the figure-eight loop makes an angle of ∼79.73° with each other, the fluorene moieties maintained their own planarity, and one of the fluorene moieties was not involved in conjugation with the rest of the macrocycle. The absorption spectra of hexaphyrins showed one intense sharp band in the higher energy region and a broad band in the lower energy region. The electrochemical studies indicated that expanded hexaphyrins are relatively electron-rich and showed three easier oxidations and one reduction. The DFT/TD-DFT studies are in agreement with the experimental observations.

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Carbaporphyrin Dimers That Bear a Rigid Naphthalene Motif as an Internal Strap

Cited by 17 publications

References 34 publications

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds

Synthesis, Structure, and Optical Properties of a Bis-Macrocycle Derived from a Highly Emissive 1,3,6,8-Tetra(1H-pyrrol-2-yl)pyrene

Bis-(Fluorene)-Embedded Hexaphyrins

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