Cyclic polyacetylene

Miao, Zhihui; Gonsales, Stella A.; Ehm, Christian; Mentink-Vigier, Frédéric; Bowers, Clifford R.; Sumerlin, Brent S.; Veige, Adam S.

doi:10.1038/s41557-021-00713-2

Cited by 61 publications

(63 citation statements)

References 69 publications

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“…31,32 Affording improved characterization and good samples of PA, precursors bearing naphthalene units are soluble and stable at room temperature. 32 Cyclic polyacetylene (c-PA) 34 is now accessible from acetylene gas and catalyst 1 35−37 (Figure 1E), but the relationships between its cyclic topology and physical, electronic, and mechanical properties are unknown. Smaller hydrodynamic volumes, lower intrinsic and melt viscosities, and higher glass transition temperatures (T g ) are properties that differ between linear and cyclic polymers.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Providing evidence of a cyclic structure remains challenging due to the insoluble nature of PA. Atomic force microscopy (AFM) images of cyclic bottlebrush derivatives of c-PA provide absolute evidence for the cyclic topology. 34,48 Another approach to confirming the cyclic topology is to first synthesize a soluble precursor and execute solution-phase structural investigations prior to forming c-PA. Herein, we report the ring-expansion metathesis polymerization (REMP) of cyclic alkenes via tungsten alkylidyne catalyst 2 49,50 to yield soluble cyclic polymer precursors to c-PA. Accessible now from a soluble and processable polymer precursor are lustrous thin films of c-PA that exhibit high conductivity when doped.…”

Section: ■ Introductionmentioning

confidence: 99%

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Soluble Polymer Precursors via Ring-Expansion Metathesis Polymerization for the Synthesis of Cyclic Polyacetylene

et al. 2021

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Cyclic polyacetylene (c-PA) is the cyclic derivative of the semiconducting linear polyacetylene. As with the linear derivative, cyclic polyacetylene is insoluble, making its characterization and processing challenging. Herein, we report the synthesis of c-PA via an indirect approach, employing ring-expansion metathesis polymerization of cyclic alkenes to form soluble polymer precursors. Subsequent retro-Diels−Alder elimination through heating provides c-PA. Dilute solution characterizations of the polymer precursors including 1 H nuclear magnetic resonance spectroscopy, gel permeation chromatography, and infrared and Raman spectroscopy confirm their cyclic structure and, by inference, the cyclic topology of the resulting c-PA. Solid-state thermal analyses via thermogravimetric analysis and differential scanning calorimetry reveal the chemical and physical transformations occurring during the retro-Diels−Alder elimination step and concurrent isomerization. Freestanding films are attainable via the soluble precursors, and when doped with I 2 , the films are semiconducting.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Soluble Polymer Precursors via Ring-Expansion Metathesis Polymerization for the Synthesis of Cyclic Polyacetylene

et al. 2021

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“…The structure imparts them with unique properties and functions that cannot be accessed by the linear analogs. [1][2][3] For example, cyclic polymers have smaller hydrodynamic volume, lower melt viscosity, higher glasstransition temperatures, and distinct self-assembly behavior. In addition, various applications of the polymers have been revealed, such as drug delivery, rheological modifiers, plasticizers, lubricants, polymer building block, supramolecular, and material chemistry.…”

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confidence: 99%

Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Gao

et al. 2022

Angewandte Chemie

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Cyclic polymers attract attention because of their endless structure and unique properties, which differ from the linear analogs. However, the synthesis of cyclic polymers is difficult and prohibits their functions and applications. In this study, we reported chiral cyclic Pd II -catalysts that initiate a living ring-expansion polymerization of isocyanides, yielding a single-handed cyclic-helical poly(phenyl isocyanide), with predictable molecular weight (M n ) and low dispersity (M w /M n ), in good yield. Using this method, cyclic bottlebrush polymers were prepared via the grafting-onto strategy. The cyclic topology was confirmed using various spectroscopic data and atomic force microscope observation. Moreover, the cyclic polymer brushes, comprising of a one-handed helical backbone, showed interesting photoluminescence and circularly-polarized luminescence.

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“…23 The recent synthesis of cyclic poly(acetylene) demonstrated by Veige and Sumerlin has further piqued the interest of researchers to delve deeper into conjugated cyclic polymer synthesis. 24 While smallmolecule cyclic conjugated materials are well precedented, 25,26 the exploration of analogous macromolecules deserves further attention. Combining the desirable physical properties (e.g., lower chain entanglement) of cyclic polymers alongside well-studied conjugated polymer motifs 27 will uncover new materials science phenomena.…”

Section: Synpacts Synlettmentioning

confidence: 99%

Ring-Expansion Metathesis Polymerization Initiator Design for the Synthesis of Cyclic Polymers

Golder¹,

Morrison²

2022

Synlett

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Cyclic polymers are of increasing interest to the synthetic and physical polymer communities due to their unique structures that lack chain ends. This topological distinction results in decreased chain entanglement, lower intrinsic viscosity, and smaller hydrodynamic radii. Many methods for the production of cyclic polymers exist, however, large-scale production of architecturally pure cyclic polymers is challenging. Ring-expansion metathesis polymerization (REMP) is an increasingly promising method to produce cyclic polymers because of the mild and scalable reaction conditions. Herein, a brief history of REMP for the synthesis of cyclic polymers with both ruthenium and non-ruthenium initiators is discussed. Even though REMP is a promising method for synthesizing cyclic polymers, state-of-the-art methods still struggle with poor molar mass control, slow polymerization rates, low conversion, and poor initiator stability. To combat these challenges, our group has developed a tethered ruthenium-benzylidene initiator, CB6, which utilizes design features from ubiquitous Grubbs-type initiators used in linear polymerizations. These structural modifications are shown to improve initiator kinetics, enhance initiator stability, and increase control over the molar mass of the resulting cyclic polymers.1 Introduction2 Ring-Expansion Metathesis Polymerization (REMP) with Ruthenium Initiators3 New Developments in Ruthenium Ring-Expansion Metathesis (REMP) Initiator Design4 Ring-Expansion Metathesis Polymerization (REMP) with Non-Ruthenium Initiators5 Conclusions

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Cyclic polyacetylene

Cited by 61 publications

References 69 publications

Soluble Polymer Precursors via Ring-Expansion Metathesis Polymerization for the Synthesis of Cyclic Polyacetylene

Soluble Polymer Precursors via Ring-Expansion Metathesis Polymerization for the Synthesis of Cyclic Polyacetylene

Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Ring-Expansion Metathesis Polymerization Initiator Design for the Synthesis of Cyclic Polymers

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