Synthesis, Characterization, and Electron‐Transport Properties of a π‐Conjugated Heteromacrocycle: A Selenium‐Bridged Neutral Annulene

Liu, Huan; Qin, Yunke; Xu, Wei; Zhu, Daoben

doi:10.1002/ajoc.201402157

Cited by 3 publications

(4 citation statements)

References 24 publications

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“…The proton NMR spectrum revealed the diatropic ring current effects expected of the 4nπ system. Surprisingly, they could predict the possibility of 20π antiaromatic dication [91] ++ upon the addition of H 2 SO 4 to 91.…”

Section: Expanded Isophlorins With Ethylene Bridgesmentioning

confidence: 98%

“…Further investigations revealed the reduction of these aromatic dications to the corresponding antiaromatic free base upon the addition of reducing agents such as FeCl 2 , Zn, or triethyl amine. Similar structural modifications to the isophlorin structure, 43 , were reported by the groups of Kamljit Singh and Daoben Zhu …”

Section: π Extended Isophlorinoidsmentioning

confidence: 99%

“…Similar structural modifications to the isophlorin structure, 43, were reported by the groups of Kamljit Singh 90 and Daoben Zhu. 91 They synthesized an aromatic 22π expanded isophlorin, 91, with four thiophene units by replacing two meso carbons with equal ethylene bridges (Scheme 44). McMurry coupling of (phenylmethylene)dithiophene/selenophene dialdehyde followed by DDQ oxidation yielded the corresponding 22π expanded isophlorin.…”

Section: Expanded Isophlorins With Ethylene Bridgesmentioning

confidence: 99%

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Isophlorinoids: The Antiaromatic Congeners of Porphyrinoids

et al. 2016

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Ever since the discovery of the porphyrin ring in "pigments of life", such as chlorophyll and hemoglobin, it has become a prime synthetic target for optoelectronic properties and in the design of metal complexes. During one such early expedition on the synthesis of porphyrin, Woodward proposed that condensing pyrrole with an aldehyde under acidic conditions yields the "precursor" porphyrinogen macrocycle. Its four-electron oxidation leads to the "transitory" 20π isophlorin, which undergoes subsequent two-electron oxidation to form the 18π "porphyrin". Due to its fleeting lifetime, it has been a synthetic challenge to stabilize the tetrapyrrolic isophlorin. This macrocycle symbolizes the antiaromatic character of a porphyrin-like macrocycle. In addition, the pyrrole NH also plays a key role in the proton-coupled, two-electron oxidation of isophlorin to the aromatic porphyrin. However, a major aspect of its unstable nature was attributed to its antiaromatic character, which is understood to destabilize the macrocycle upon conjugation. Antiaromaticity in general has not gained significant attention mainly due to the lack of stable 4nπ systems. In this regard, a stable isophlorin and its derivatives provide a glimmering hope to peek into the world of antiaromatic systems. This review will focus on the attempted synthesis of antiaromatic isophlorin ever since its conception. Based on recent synthetic advances, the chemistry of isophlorins can be expected to blossom into expanded derivatives of this antiaromatic macrocycle. Along with the synthetic details, the structural, electronic, and redox properties of isophlorin and its expanded derivatives will be elaborated.

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Section: Expanded Isophlorins With Ethylene Bridgesmentioning

confidence: 98%

Section: π Extended Isophlorinoidsmentioning

confidence: 99%

Section: Expanded Isophlorins With Ethylene Bridgesmentioning

confidence: 99%

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Isophlorinoids: The Antiaromatic Congeners of Porphyrinoids

et al. 2016

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“…6 However, stable expanded isophlorins are achieved by interlinking heterocyclic units (thiophene, furan and/or selenophene) through bridging carbon atoms with a conjugation flow only through the carbon atoms. 7 Recently, non-antiaromatic cycloparaphenylene macrocycles 8 1 with all benzenoid forms exhibited local to global aromaticity when they were oxidized to their dicationic quinoidal forms 2 (Fig. 1).…”

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confidence: 99%

Reversible redox switching between local and global aromaticity for core-modified expanded carbaisophlorinoids

et al. 2022

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A flexible expanded heterocorrole: Tellura[22]porphyrin(6.1.1.0)

Hojniak-Thyssen

Szczepaniak

Latos‐Grażyński

et al. 2019

J. Porphyrins Phthalocyanines

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An expanded heterocorrole, meso-tetraaryl-tellura[22]porphyrin(6.1.1.0), containing a bipyrrole moiety and a six-carbon long link, has been synthesized. The reaction path proceeds through a controlled acid-promoted extrusion of one tellurium atom from meso-aryl-26,28-ditellurasapphyrin, leading to a structure where one tellurophene ring of the substrate is replaced by a bridging acyclic four-carbon unit. This aromatic porphyrin-annulene hybrid is conformationally flexible in solution, on account of the C4 unit adopting two different configurations: trans–cis–trans or all-trans. Studies of the dynamic behavior of tellura[22]porphyrin(6.1.1.0) in solution were performed by means of 1H and 125Te NMR spectroscopy. The X-ray structure of the all-trans form with trapezoid macrocyclic skeleton is also presented.

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Synthesis, Characterization, and Electron‐Transport Properties of a π‐Conjugated Heteromacrocycle: A Selenium‐Bridged Neutral Annulene

Abstract: 10 À3 cm 2 V À1 S À1 and the on/off ratio of 1.0 10 5 . The thin-film morphology of devices based on DPTSA was also characterized to preliminarily reveal the structure-property relationships.

Cited by 3 publications

References 24 publications

Isophlorinoids: The Antiaromatic Congeners of Porphyrinoids

Isophlorinoids: The Antiaromatic Congeners of Porphyrinoids

Reversible redox switching between local and global aromaticity for core-modified expanded carbaisophlorinoids

A flexible expanded heterocorrole: Tellura[22]porphyrin(6.1.1.0)

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