Synthesis and Photophysical Properties of Carbazole-Functionalized Diazaphosphepines via Sequent P–N Chemistry

Li, Xinyu; Liu, Zhaoxin; Li, Can; Gao, Rong; Qi, Yanpeng; Ren, Yi

doi:10.1021/acs.joc.3c01351

J. Org. Chem.

2023

DOI: 10.1021/acs.joc.3c01351

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Synthesis and Photophysical Properties of Carbazole-Functionalized Diazaphosphepines via Sequent P–N Chemistry

Xinyu Li,

Zhaoxin Liu,

Can Li

et al.

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Cited by 5 publications

(2 citation statements)

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“…Seven-membered phosphorus heterocycles (7MPHs) are among the least explored types of these systems . Despite recent publications highlighting the synthesis and research on π-conjugated variants and chiral ligands, access to 7MPHs remains limited . Leveraging phosphorus heterocycles with smaller rings as initial substrates for the synthesis of 7MPHs is an attractive approach, achievable through ring enlargement, and several successful examples of this strategy are documented in the literature .…”

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confidence: 99%

Phenoxaphosphonium Mixed Ylides in Ring Expansion Reaction

Nenashev,

Dospekhov,

Zavaruev

et al. 2024

J. Org. Chem.

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Treatment of mixed phosphonium−iodonium ylides featuring a six-membered phenoxaphosphonium fragment with aqueous tetrafluoroboronic acid induces a rearrangement, resulting in expansion of the phosphacycle and oxidation of the phosphorus atom. The target difficult-to-access dibenzo[b,f ][1,4]oxaphosphepine oxides (3 examples) were isolated in excellent yields (up to 95%) as mixtures of stereoisomers. Hydrolysis of a five-membered mixed ylide, a dibenzophosphole derivative, predominantly preserves the phosphole system with cycle expansion occurring as a side process.

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mentioning

confidence: 99%

Phenoxaphosphonium Mixed Ylides in Ring Expansion Reaction

Nenashev,

Dospekhov,

Zavaruev

et al. 2024

J. Org. Chem.

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“…Recently, functionalized phosphepines started to draw attention in the perspective of photophysical properties, redox properties and optoelectronic properties. [36][37][38][39][40] In 2019, Hissler and coworkers reported the first example of thiophene functionalized phosphepine 7a (Figure 2). 37 Presence of thiophene moiety allowed 7a to be readily functionalized with various aryl groups (7b-d, Figure 2).…”

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Design of Indole-Functionalized Phosphepines towards New Organic Chromophores

Ren,

Liu

2023

Synlett

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Organic chromophores emerged as diverse functional materials in the areas of organic catalysis, toxic materials sensing, bio-imaging, and organic electronic devices. With rich chemical and electronic structures, main-group elements were extensively implanted in organic chromophores to fine tune the chemical/electronic structures and optoelectronic properties. In this synpact article, we present a concise overview about the development of phosphorus (P)-containing organic chromophores, further highlighting our recent contribution in the field. A new aspect of combining P element and indole moiety was pursued to construct a new series of seven-membered P-organic chromophores, namely indole-functionalized phosphepines. The new combination endowed the system with rich chemical and electronic structures, in which intriguing photophysical properties were consequently revealed. The combination not only provided an efficient synthetic protocol to access new P-heterocycles, also as offered a new strategy to design functional organic chromophores.

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Dithieno[3,2‐b; 2′,3′‐f]phosphepinium‐Based Near‐Infrared Fluorophores: p_x–π* Conjugation Inherent to Seven‐Membered Phosphacycles

Andoh,

Murai,

Bouit

et al. 2024

Angewandte Chemie

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Positively charged phosphorus‐containing heterocycles are characteristic core skeletons for functional molecules. While various phosphonium‐containing five‐ or six‐membered ring compounds have been reported, seven‐membered ring phosphepinium has not yet been fully studied. In this study, dithieno[2,3‐b;3,2‐f]phosphepinium ions containing electron‐donating aminophenyl groups were synthesized. An X‐ray crystallographic analysis of the resulting donor‐acceptor‐donor dyes revealed a bent conformation of the central seven‐membered ring. This compound exhibited fluorescence in the near‐infrared region with a bathochromic shift of 70 nm compared to phosphepine oxide congener and a large Stokes shift. High fluorescence quantum yields were obtained even in polar solvents due to the suppression of the nonradiative decay process. The theoretical study revealed that the phosphepinium skeleton is highly electron‐accepting owing to the orbital interaction between a px orbital of the phosphonium moiety and a π* orbital of the 1,3,5‐hexatriene moiety. Owing to the lower‐lying px orbital in the phosphonium moiety compared with that of the phosphine oxide and the bent conformation of the seven‐membered ring, the phosphepinium ring effectively furnishes a px‐π* conjugation. A large structural relaxation with the contribution of a quinoidal resonance structure is suggested in the excited state, which is responsible for the intense emission with a large Stokes shift.

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Synthesis and Photophysical Properties of Carbazole-Functionalized Diazaphosphepines via Sequent P–N Chemistry

Cited by 5 publications

References 59 publications

Phenoxaphosphonium Mixed Ylides in Ring Expansion Reaction

Phenoxaphosphonium Mixed Ylides in Ring Expansion Reaction

Design of Indole-Functionalized Phosphepines towards New Organic Chromophores

Dithieno[3,2‐b; 2′,3′‐f]phosphepinium‐Based Near‐Infrared Fluorophores: p_x–π* Conjugation Inherent to Seven‐Membered Phosphacycles

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Synthesis and Photophysical Properties of Carbazole-Functionalized Diazaphosphepines via Sequent P–N Chemistry

Cited by 5 publications

References 59 publications

Phenoxaphosphonium Mixed Ylides in Ring Expansion Reaction

Phenoxaphosphonium Mixed Ylides in Ring Expansion Reaction

Design of Indole-Functionalized Phosphepines towards New Organic Chromophores

Dithieno[3,2‐b; 2′,3′‐f]phosphepinium‐Based Near‐Infrared Fluorophores: px–π* Conjugation Inherent to Seven‐Membered Phosphacycles

Contact Info

Product

Resources

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Dithieno[3,2‐b; 2′,3′‐f]phosphepinium‐Based Near‐Infrared Fluorophores: p_x–π* Conjugation Inherent to Seven‐Membered Phosphacycles