Phenanthriporphyrin: An Antiaromatic Aceneporphyrinoid as a Ligand for a Hypervalent Organophosphorus(V) Moiety

32-Hetero-5,6-dimethoxyphenanthrisapphyrins-macrocycles that link structural features of polycylic aromatic hydrocarbons and expanded porphyrins-were obtained in a straightforward [3+1] condensation reaction of dimethoxyphenanthritripyrrane and 2,5-bis(arylhydroxymethyl)heterocyclopentadienes. The highly folded conformation of formally 4 n π-electron macrocycles causes them to manifest only limited macrocyclic π conjugation as explored by means of NMR spectroscopic and X-ray structural analyses, and supported by DFT calculations. Although protonation does not change their π-conjugation characteristics, the cleavage of ether groups at the phenanthrenylene moiety yields nonaromatic 32-hetero-5,6-dioxophenanthrisapphyrins.

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“…3,6‐Bis(phenyl‐(2‐pyrolyl)hydroxymethyl)‐9,10‐dimethoxyphenanthrene ( 1 ) : Compound 1 was synthesized according to a literature procedure …”

Section: Methodsmentioning

confidence: 99%

Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids

Szyszko

Małecki

Berlicka

et al. 2016

Chemistry A European J

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“…Latos-Grażyński and co-workers synthesized phenanthrene moiety incorporated macrocycle, 3,6-phenanthriporphyrin 40 exhibiting the structural features of both phenanthrene and porphyrin (Scheme 8). [12] The precursor, 3,6-dibenzoyl-9,10dimethoxyphenanthrene 42 was synthesized by reacting 9,10dimethoxyphenanthrene 41 with benzoyl chloride in 1,2dichloroethane in the presence of AlCl 3 . The reduction of 42 with sodium borohydride yielded the diol 43, which was reacted with pyrrole in the presence of BF 3 · OEt 2 to form phenanthritripyrrane 44.…”

Section: B Porphyrinoids With Two Adjacent Pyrrole Rings Substitutedmentioning

confidence: 99%

Polycyclic Aromatic Hydrocarbon‐/Heterocycle‐Embedded Porphyrinoids

2020

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Porphyrinoids in which one or two pyrrole rings are replaced with polycyclic aromatic hydrocarbons/heterocycles such as naphthalene, phenanthrene, biphenyl, bipyridine, or phenanthroline are a new class of porphyrinoids represented as polycyclic aromatic hydrocarbon (PAH)‐/heterocycle‐embedded porphyrinoids. These macrocycles possess the structural features of both polycyclic aromatic hydrocarbons/heterocycles and cyclic polypyrrolic porphyrinoids. The PAH‐embedded porphyrinoids have drawn significant interest in recent times because of the following: (1) these macrocycles exhibit different π‐conjugation pathways unlike porphyrinoids, which exhibit circular conjugation pathways in their macrocyclic rings with various molecular structures; (2) the PAHs embedded macrocycles show variable degree of aromaticity which varies from weak aromaticity to antiaromaticity and (3) the PAHs embedded porphyrinoids provide unique ligand environment to form stable coordination and organometallic complexes in which metals may show uncommon oxidation states and unusual reactivity. All these above‐listed features depend on polycyclic aromatic hydrocarbon/heterocycle moiety present as a part of porphyrinoid macrocyclic framework. This Minireview focuses on the synthesis of different polycyclic aromatic hydrocarbon‐/heterocycle‐embedded porphyrins, contracted porphyrins and expanded porphyrins and briefly discusses their structural, spectral, aromatic and coordination properties.

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“…93 Phenanthrene dicarbinol 179 was reacted with excess pyrrole and BF 3 ·Et 2 O to give tripyrrane analogue 180, and this was cyclized with benzaldehyde and BF 3 ·Et 2 O and then oxidized with 2 equivalents of DDQ to give phenanthriporphyrin 178. 93 Phenanthrene dicarbinol 179 was reacted with excess pyrrole and BF 3 ·Et 2 O to give tripyrrane analogue 180, and this was cyclized with benzaldehyde and BF 3 ·Et 2 O and then oxidized with 2 equivalents of DDQ to give phenanthriporphyrin 178.…”

Section: Dibenziporphyrins and Related Dicarbaporphyrinoidsmentioning

confidence: 99%

Benziporphyrins, a unique platform for exploring the aromatic characteristics of porphyrinoid systems

2015

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Benziporphyrins were first discovered over 20 years ago. Although initially they were considered to be a chemical curiosity, a wide range of benzene-containing porphyrinoid systems are now known that exhibit intriguing spectroscopic, structural and chemical properties. These systems can often generate stable organometallic derivatives, and have been shown to have applications in the development of chemical sensors and in molecular recognition studies. The characteristics of these porphyrinoid macrocycles vary from nonaromatic to highly aromatic systems, and in a few cases antiaromatic structures are formed. The variations in aromatic character are insightful and provide a deeper understanding of aromaticity and conjugation in porphyrinoid structures. In this review, the synthesis and properties of benziporphyrinoid systems is presented with a particular emphasis on the variations in aromatic characteristics.

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Phenanthriporphyrin: An Antiaromatic Aceneporphyrinoid as a Ligand for a Hypervalent Organophosphorus(V) Moiety

Cited by 88 publications

References 35 publications

Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids

Incorporation of a Phenanthrene Subunit into a Sapphyrin Framework: Synthesis of Expanded Aceneporphyrinoids

Polycyclic Aromatic Hydrocarbon‐/Heterocycle‐Embedded Porphyrinoids

Benziporphyrins, a unique platform for exploring the aromatic characteristics of porphyrinoid systems

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