Tetraarylphosphonium polyelectrolyte chromophores: synthesis, stability, photophysics, film morphology and critical surface energy

Bedford, Monte S.; Yang, Xiaoyan; Jolly, Kara M.; Binnicker, Rachel L.; Cramer, Samuel B.; Keen, Caitlin E.; Mairena, Connor J.; Patel, Amar; Rivenbark, Meredith T.; Galabura, Yuriy; Luzinov, Igor; Smith, Rhett C.

doi:10.1039/c4py01483a

Cited by 19 publications

(18 citation statements)

References 69 publications

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“…6 Second, an S N Ar pathway, with PPh 3 as a leaving group (Fig. 2, path B), 7 is also possible, and mechanistic studies into this reaction are ongoing in our laboratory.…”

Section: Resultsmentioning

confidence: 99%

Selective formation of heteroaryl thioethers via a phosphonium ion coupling reaction

2018

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Heteroaryl thioethers, comprised of pyridines and diazines, are an important class of compounds with relevance to medicinal chemistry. Metal-catalyzed cross-couplings and SNAr are traditionally used to form C–S bonds in these systems but are limited by available halogenated precursors. An alternative approach is presented where pyridines and diazines are transformed into heterocyclic phosphonium salts and then C–S bonds are formed by adding thiolate nucleophiles. The process is 4-selective for pyridines, simple to execute and can be used to make derivatives of complex pharmaceuticals.

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“…6 Second, an S N Ar pathway, with PPh 3 as a leaving group (Fig. 2, path B), 7 is also possible, and mechanistic studies into this reaction are ongoing in our laboratory.…”

Section: Resultsmentioning

confidence: 99%

Selective formation of heteroaryl thioethers via a phosphonium ion coupling reaction

2018

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“…On the basis of our prior work with linear tetraarylphosphonium polymers, we expected P1 to have good thermal stability. TGA was thus applied to probe the thermal stability of P1 .…”

Section: Resultsmentioning

confidence: 99%

A new route to phosphonium polymer network solids via cyclotrimerization

Yang

Wen

Chumanov

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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An organo‐main group network solid having tetrahedral phosphonium vertices was prepared from a diacetyl monomer via a straightforward cyclotrimerization reaction. The network solid composition was examined by FT‐IR spectroscopy and elemental microanalysis, revealing quantitative reaction of carbonyl moieties and a 67% degree of cross‐linking. The reaction yielded a material having a layered structure that is comprised of an amorphous polymer and which is thermally stable up to 370 °C in air with a char yield of 40% upon heating as high as 800 °C under N2. The polymer is stable to 6 M NaOH(aq) at 60 °C for 24 h and takes up only 10.63% of water by mass at room temperature. The surface morphology, as examined by AFM, revealed a very smooth as‐prepared film (RMS roughness of 3 nm). The specific surface area measured by BET analysis with N2 gas is 9 m2 g−1, indicating a type II, nonporous material. Physisorption with CO2 revealed that the phosphonium network solid has additional affinity for CO2, suggesting that such materials may have use for applications such as CO2 capture. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1620–1625

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“…Compared to polyelectrolytes bearing alkyl phosphonium sites, tetraaryl phosphonium polyelectroplytes (TPELs) have demonstrated significantly improved thermal and chemical (particularly alkaline) stability …”

Section: Introductionmentioning

confidence: 99%

Convenient synthetic route to tetraarylphosphonium polyelectrolytes via palladium‐catalyzed P–C coupling of aryl triflates and diphenylphosphine

Wan

Yang

Smith

2017

J. Polym. Sci. Part A: Polym. Chem.

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A series of eight tetraarylphosphonium polyelectrolytes (TPELs) has been successfully synthesized by polymerization of diphenylphosphine and bis(aryl triflate)s. The bis(aryl triflate)s are readily prepared from bisphenols, some of which are commodity feedstocks such as bisphenol A. The polymerization via palladium catalyzed P-C bond formation produces degrees of polymerization up to 65. All polymeric triflates have reasonable thermal stability in the range of 350-450 8C. The stability of the TPELs to alkaline solution is strongly depending on the spacer between adjacent phosphonium sites. Polymers with electron-releasing and bulky substituent para-to the phosphonium site have improved stability while those with electron-withdrawing substituent para-to phosphonium site have decreased alkaline stability due to decomposition via a nucleophilic aromatic substitution pathway. These findings have important ramifications for the design of ionomers for alkaline exchange membrane fuel cells and related electrochemical energy conversion devices.

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Tetraarylphosphonium polyelectrolyte chromophores: synthesis, stability, photophysics, film morphology and critical surface energy

Abstract: Chromophore-modified polymers with tetraarylphosphonium units in the main chain have been prepared by a Ni-catalysed P–C bond-forming reaction.

Cited by 19 publications

References 69 publications

Selective formation of heteroaryl thioethers via a phosphonium ion coupling reaction

Selective formation of heteroaryl thioethers via a phosphonium ion coupling reaction

A new route to phosphonium polymer network solids via cyclotrimerization

Convenient synthetic route to tetraarylphosphonium polyelectrolytes via palladium‐catalyzed P–C coupling of aryl triflates and diphenylphosphine

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