<i>Bis‐</i>(Dibenzothiophene) Embedded Hexaphyrins: Synthesis, Structure and Properties

Sinha, Abhas Kumar; Kumar, Ankit; Ravikanth, Mangalampalli

doi:10.1002/ajoc.202100157

Cited by 5 publications

(3 citation statements)

References 43 publications

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“…The same group reported the heterocyclic analogs of 5, namely dibenzofuran-6 and dibenzothiophene-embedded 7 porphyrinoids (Scheme 22). [47,83] The synthetic methodologies relied on the same principle: condensing the proper tripyrrane analog with aromatic aldehyde, followed by oxidation with DDQ. Both macrocycles demonstrated NMR spectroscopic features expected of nonaromatic porphyrinoids.…”

Section: Fluorenophyrinsmentioning

confidence: 99%

Phenanthrene‐Embedded Carbaporphyrinoids and Related Systems: From Ligands to Cages and Molecular Switches

Szyszko

2022

Eur J Org Chem

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This Review discusses the recent developments in the field of synthetic chemistry of PAH–porphyrin hybrids, emphasizing phenanthrene‐embedded carbaporphyrinoids and related systems. The discussion covers various aspects of phenanthriporphyrin and its derivates chemistry, including their spectroscopic features, aromaticity, core reactivity, and coordination properties. The development of expanded phenanthriporphyrinoids is outlined, followed by the presentation of related carbaporphyrinoids incorporating hydrocarbon moieties such as fluorene, biphenyl, terphenyl, and dibenzo[g,p]chrysene. The exploitation of phenanthriporphyrinoids as a unique class of ligands for organometallic chemistry is discussed, altogether with their use for the construction of conformational and stereochemical switches. The perspective for using related macrocycles as building blocks for carbaporphyrinoid cages is also outlined.

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Section: Fluorenophyrinsmentioning

confidence: 99%

Phenanthrene‐Embedded Carbaporphyrinoids and Related Systems: From Ligands to Cages and Molecular Switches

Szyszko

2022

Eur J Org Chem

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“…[6,7] In recent times, polycyclic aromatic hydrocarbon/heterocycle (PAH) embedded porphyrinoids have received significant attention due to their unique properties exhibiting the features of both PAH and porphyrinoids. Different polycyclic aromatic hydrocarbons/ heterocycles such as naphthalene, [8] dibenzofuran/ thiophene, [9,10] anthracene, [11] pyrene, [12] fluorene, [13,14] bipyridine, [15] phenanthroline, [16] phenothiazine, [17a-c] and so on have been incorporated into the framework of porphyrinoid in place of one or two pyrrole/heterocycle rings and explored their electronic and structural properties. Among different polycyclic aromatic heterocycles, phenothiazine (PTZ) is very important as this heterocycle is widely used in the synthesis of various organic dyes [18] such as methylene blue, [19] methylene green, [20] thionine [21] and also in certain pharmaceutical drugs such as chlorpromazine [22] and so on.…”

Section: Introductionmentioning

confidence: 99%

Phenothiazine Embedded Dithiasmaragdyrins

Tripathi,

Dutta,

Yadav

et al. 2024

Chemistry An Asian Journal

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Two different types of novel phenothiazine‐embedded dithiasmaragdyrins containing one phenothiazine ring, two thiophene rings and two pyrrole rings connected via three meso carbons and two direct bonds in the macrocyclic framework were synthesized over the sequence of synthetic steps starting with phenothiazine. Three examples of phenothiazine‐embedded dithiasmaragdyrins were synthesized by condensing appropriate phenothiazine‐based pentapyrrane with pentafluorobenzaldehyde and two examples of phenothiazine sulfone embedded dithiasmaragdyrins were synthesized by condensing phenothiazine‐based diol with appropriate meso‐aryl dipyrromethane under mild acid‐catalysed conditions. 1D & 2D NMR studies revealed that the thiophene rings adopted inverted orientation in phenothiazine sulfone embedded dithiasmaragdyrins whereas in phenothiazine‐embedded dithiasmaragdyrins, the thiophene rings were in normal orientation. Both types of macrocycles exhibit nonaromatic absorption features and showed panchochromic absorption features in its neutral and protonated forms. The electrochemical studies indicated that the phenothiazine‐embedded dithiasmaragdyrins were more electron‐rich compared to phenothiazine sulfone embedded dithiasmaragdyrins. DFT studies revealed that both types of dithiasmaragdyrins exhibit significantly distorted structures and TD‐DFT studies support the experimental observations.

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“…In 2017, we reported the first example of a DBT-based nonaromatic hybrid macrocycle 2 , which exhibits features of both contracted macrocycles, subporphyrins, and triphyrin(2.1.1)s, and the macrocycle was used as a ligand to synthesize the Re(I) complex . Subsequently, we synthesized different DBT-containing porphyrinoids such as DBT-containing heteroporphyrins 3 , DBT-containing dithia-bis(calix)sapphyrins 4 , and bis(dibenzothiophene)-containing hexaphyrins 5 (Chart ) and explored their structure and spectral, redox, and coordination properties. − Some of these macrocycles absorb strongly in the visible–NIR region and exhibit very interesting features. Herein, we report a new type of hexaphyrin macrocycles 6 – 8 consisting of two p -phenylene, two pyrroles, one thiophene, and one dibenzothiophene unit connected in a macrocyclic framework via four meso carbons and two direct bonds over a sequence of six simple steps starting with commercially available dibenzothiophene.…”

Section: Introductionmentioning

confidence: 99%

Dibenzothiophene-Containing Thiacarbaporphyrinoids

Kaur,

Rawat,

Ravikanth

2023

J. Org. Chem.

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A new type of expanded dibenzothiophene-containing thiacarbaporphyrinoid containing one dibenzothiophene, two p-phenylene, one thiophene, and two pyrrole rings connected via four meso carbons and two direct bonds was synthesized over a sequence of six steps starting with commercially available dibenzothiophene. The X-ray structure obtained for one of the macrocycles revealed that the macrocycle was very nonplanar and the two p-phenylene rings and dibenzothiophene unit were deviated from the mean plane, whereas the thiophene ring attained inverted conformation and was facing toward outside the macrocyclic core. The X-ray structure also revealed that the dibenzothiophene unit of the macrocycle maintained its π-electron delocalization and did not extend the π-electron delocalization with the rest of the macrocycle, and the effective π-conjugation was present only in the lower part of the macrocyclic core, i.e., the thiatripyrrin moiety. The spectral and theoretical studies support the nonaromatic nature of the macrocycles. The macrocycles exhibit one strong absorption band at ∼430 nm and one broad absorption band in the 500–800 nm region, which were bathochromically shifted in diprotonated derivatives which absorb strongly in the visible–NIR region. The electrochemical studies indicated the electron-rich nature of the macrocycles and the theoretical studies corroborated the experimental observations.

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Bis‐(Dibenzothiophene) Embedded Hexaphyrins: Synthesis, Structure and Properties

Cited by 5 publications

References 43 publications

Phenanthrene‐Embedded Carbaporphyrinoids and Related Systems: From Ligands to Cages and Molecular Switches

Phenanthrene‐Embedded Carbaporphyrinoids and Related Systems: From Ligands to Cages and Molecular Switches

Phenothiazine Embedded Dithiasmaragdyrins

Dibenzothiophene-Containing Thiacarbaporphyrinoids

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