An improved synthesis of poly(p-phenylenebutadiynylene)s

Williams, Vance E.; Swager, Timothy M.

doi:10.1002/1099-0518(200012)38:1+<4669::aid-pola60>3.0.co;2-w

Cited by 32 publications

(9 citation statements)

References 33 publications

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“…Because the structure of the polymers is nominally identical, the difference in photophysical properties must arise from differences in backbone or end-group structures (or defects) that result from the difference in polymerization method. An important feature of the chain-growth polymerization is that the catalyst from the initial catalyst–monomer complex transfers along the growing polymer chain, and this process may give rise to increased integrity of the phenylene ethynylene polymer backbone structure (e.g., minimizing butadiyne and other structural defects). − A shortcoming of copper-mediated Sonagashira coupling is the formation of butadiyne defects resulting from acetylene homocoupling . Moreover, a previous report indicated that poly( p -phenylenebutadiynylene)s (PPBs) obtained from homocoupling of 1,4-diethynylbenzene derivatives were only sparingly soluble .…”

Section: Resultsmentioning

confidence: 99%

“…An important feature of the chain-growth polymerization is that the catalyst from the initial catalyst–monomer complex transfers along the growing polymer chain, and this process may give rise to increased integrity of the phenylene ethynylene polymer backbone structure (e.g., minimizing butadiyne and other structural defects). − A shortcoming of copper-mediated Sonagashira coupling is the formation of butadiyne defects resulting from acetylene homocoupling . Moreover, a previous report indicated that poly( p -phenylenebutadiynylene)s (PPBs) obtained from homocoupling of 1,4-diethynylbenzene derivatives were only sparingly soluble . However, the UV–visible absorption and fluorescence spectra of these PPBs were similar to those of typical PPE-type polymers.…”

Section: Resultsmentioning

confidence: 99%

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Poly(phenylene ethynylene) Conjugated Polyelectrolytes Synthesized via Chain-Growth Polymerization

Jagadesan

Schanze

2019

Macromolecules

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This study examines the use of Pd(0)-catalyzed chain-growth Sonogashira coupling to prepare a series of poly(phenylene ethynylene) (PPE)-type conjugated polyelectrolytes that feature alkyl sulfonate (−R-SO3 –)-solubilizing groups. The polymerization used an AB-type monomer, I–Ar–CCH, with pendant sulfonate ester units (−O–CH2CH2CH2–SO3R), wherein the ester serves as a protecting group for the sulfonate groups. The conjugated polyelectrolytes were produced by hydrolysis of the ester-protecting groups post polymerization. As a point of reference, PPE-type polymers with nominally the same structures were prepared by step-growth polymerization of the AB monomer under conventional Sonagashira conditions, as well as via AA + BB polymerization of disubstituted monomers I–Ar–I and HCC–Ar–CCH. The ester-protected polymers were characterized by gel permeation chromatography in tetrahydrofuran (THF) solution. Samples prepared by chain growth have M n values ranging from 4.6 to 7.5 kDa and have comparatively low polydispersity indices, Đ ∼ 1.1–1.2. The step-growth polymers have M n ranging from 11.3 to 13.5 kD, with higher dispersity, Đ ∼ 1.5–2.3. The photophysical properties of the samples were compared, as both the ester-protected forms (in THF solution) and the polyelectrolyte forms (in MeOH and water). In general, the polymers prepared by chain growth have higher fluorescence quantum yields and better-resolved spectra, suggesting that the chains are comparatively defect-free and do not aggregate in solution.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Poly(phenylene ethynylene) Conjugated Polyelectrolytes Synthesized via Chain-Growth Polymerization

Jagadesan

Schanze

2019

Macromolecules

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“…Unfortunately, homopolymerization of 1-anti using palladium-mediated oxidative homocoupling of acetylenes 14 was not possible, and only insoluble material could be isolated.…”

Section: Organicmentioning

confidence: 99%

Rigid Hydrophilic Structures for Improved Properties of Conjugated Polymers and Nitrotyrosine Sensing in Water

2010

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“…The synthesis of a related polymer called poly(arylenebutadiynylene) (PAB) [71] makes use of the facile way in which butadiynes (I) are formed in Scheme 5.2. Scheme 5.4 shows the mechanism of how these butadiynes can be applied to polymer synthesis.…”

Section: Synthesis Of Poly(phenylenebutadiynylenes) Ppbsmentioning

confidence: 99%

“…In contrast to the Sonogashira reaction where the amine base is required in stoichiometric quantities, here the amine acts as a proton transfer catalyst. Kijima and coworkers first reported the synthesis of short polymers with this palladium-mediated cycle using I 2 as an oxidant [72,73] Swager showed benzoquinone to be a more effective oxidant as it is mild and does not react with the acetylene moiety [71]. 1) The functional group tolerance matches that of Sonogashira methods and can provide even higher molecular weight polymers by comparison (Eq.…”

Section: Synthesis Of Poly(phenylenebutadiynylenes) Ppbsmentioning

confidence: 99%