Functional phenylethynylene side arm poly(arylene ethynylene) conjugated polymers: optical and electrochemical behavior for enrichment of electronic applications

Kumar, Gunasekaran Arun; Priya, P. Gomathi; Alagar, M.

doi:10.1039/c7nj04292b

Cited by 3 publications

(2 citation statements)

References 72 publications

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“…The HOMO energy levels of copolymers were calculated from the onset of the oxidation peak in reference to the ferrocene oxidation potential. The LUMO energy levels are calculated by combining the HOMO value and optical band gap (Table ) following the previous literature − (note: a few research groups − have shown that combining optical absorption data and electrochemical redox potentials is not the best way to determine frontier energy levels because both of these are different physical processes). The free energy difference for the electron transfer from polymer to the TCNQ was determined using the Rehm–Weller equation .…”

Section: Results and Discussionmentioning

confidence: 99%

Controlling π-Conjugated Polymer–Acceptor Interactions by Designing Polymers with a Mixture of π-Face Strapped and Nonstrapped Monomers

et al. 2023

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Controlling π-conjugated polymer–acceptor complex interaction, including the interaction strength and location along the polymer backbone, is central to organic electronics and energy applications. Straps in the strapped π-conjugated polymers mask the π-face of the polymer backbone and hence are useful to control the interactions of the π-face of the polymer backbone with other polymer chains and small molecules compared to the conventional pendant solubilizing chains. Herein, we have synthesized a series of strapped π-conjugated copolymers containing a mixture of strapped and nonstrapped comonomers to control the polymer–acceptor interactions. Simulations confirmed that the acceptor is directed toward the nonstrapped repeat unit. More importantly, strapped copolymers overcome a major drawback of homopolymers and display higher photoinduced photoluminescence (PL) quenching, which is a measure of electron transfer from the polymer to acceptor, compared to that of both the strapped homopolymer and the conventional polymer with pendant solubilizing chains. We have also shown that this strategy applies not only to strapped polymers, but also to the conventional polymers with pendant solubilizing chains. The increase in PL quenching is attributed to the absence of a steric sheath around the comonomers and their random location along the polymer backbone, which enhances the probability of non-neighbor acceptor binding events along the polymer backbone. Thus, by mixing insulated and noninsulated monomers along the polymer backbone, the location of the acceptor along the polymer backbone, polymer–acceptor interaction strength, and the efficiency of photoinduced charge transfer are controllable compared to the homopolymers.

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Section: Results and Discussionmentioning

confidence: 99%

Controlling π-Conjugated Polymer–Acceptor Interactions by Designing Polymers with a Mixture of π-Face Strapped and Nonstrapped Monomers

et al. 2023

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“…In this way, it is possible to investigate the polymerization reaction mechanism that occurs using this reusable catalyst. Monomers 1 and 2 were synthesized according to literature procedures. − For the synthesis of monomer 3, the Sonogashira reaction was first performed, resulting in the precursor monomer 3a . The protected acetylene function is then deprotected using tetrabutylammonium fluoride (TBAF) to obtain monomer 3 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Poly(phenylene ethynylene) Using an Easily Recyclable Pd-Functionalized Magnetite Nanoparticle Catalyst

et al. 2020

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An easily recyclable catalyst has already been used in several cross-coupling reactions, resulting in many advantages compared to commonly used homogeneous catalysts. Despite all these implementations of such removable catalysts, it has never been performed in the synthesis of conjugated polymers. Therefore, a Pd-functionalized magnetite nanoparticle was succesfully 2 synthesized and implemented in the synthesis of poly(phenylene ethynylene). The polymerization was performed using either an AB-monomer or A2/B2 monomers, and occurred in a classical stepgrowth fashion. Mn values over 10 kg/mol were obtained. Due to the presence of the magnetite nanoparticle, the catalyst could be removed and reused up to five times using magnetic precipitation. In addition, it reduces the amount of impurities present in the polymer, as a result of the Pd-catalyst, for up to 10 times compared to a commonly used homogeneous catalyst such as Pd(PPh3)4.

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Filling the Gap within 10‐Membered Heteroenediynes: Thiaenediyne – An Experimental and Theoretical Study

Danilkina,

Khmelevskaya,

Shtyrov

et al. 2024

Eur J Org Chem

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The heteroatom nature in 10‐membered enediynes plays a crucial role in tuning of their reactivity in the Bergman cyclization, which is a decisive factor for the biological activity of enediynes. Although benzothiophene‐fused O‐ and N‐enediynes have been identified as promising biological objects, the corresponding thiaenediyne remains unknown. To fill this gap, we synthesized the thiaanalog and studied it in both practical and theoretical terms. While the Nicholas reaction has proven to be an effective cyclization technique for the preparation of heteroenediynes, in the case of thiaenediyne it was accompanied by an unusual acid‐promoted intramolecular cyclization, forming a thiepinium salt. The S‐enediyne has reduced reactivity in the Bergman cyclization relative to the N‐ and O‐enediynes, attributed to the diminished alkyne bending and extended cd‐distance. The NBO analysis of the entire series, namely the evaluation of πin/out(C2‐CC)→σ*(C−X) hyperconjugation, revealed that the S atom in S‐enediyne provides stronger stabilization of the initial compound than the N atom in N‐enediyne, while exhibiting the weakest stabilization of the Bergman cyclization transition state. NICS values were employed to examine the change in aromaticity along the Bergman cyclization coordinate. This approach, in conjunction with the NBO analysis, provides a foundation for further rational design of unnatural enediynes.

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Functional phenylethynylene side arm poly(arylene ethynylene) conjugated polymers: optical and electrochemical behavior for enrichment of electronic applications

Abstract: The new type of poly(phenyl ethynylene) side arm conjugated polymers were synthesised with effective photophysical and electrochemical properties.

Cited by 3 publications

References 72 publications

Controlling π-Conjugated Polymer–Acceptor Interactions by Designing Polymers with a Mixture of π-Face Strapped and Nonstrapped Monomers

Controlling π-Conjugated Polymer–Acceptor Interactions by Designing Polymers with a Mixture of π-Face Strapped and Nonstrapped Monomers

Synthesis of Poly(phenylene ethynylene) Using an Easily Recyclable Pd-Functionalized Magnetite Nanoparticle Catalyst

Filling the Gap within 10‐Membered Heteroenediynes: Thiaenediyne – An Experimental and Theoretical Study

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