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Polyacetylene

Polyacetylene is a conjugated organic polymer with the chemical formula (CH)_n, consisting of a linear chain of carbon atoms connected by alternating single and double bonds, making it the simplest member of the class of conducting polymers.^[1] First synthesized in the form of a metallic-looking film in the 1970s through Ziegler-Natta polymerization of acetylene gas, it is inherently semiconducting but can achieve metallic conductivity exceeding 100,000 S/cm when doped with oxidants like iodine or reductants like alkali metals.^[2] This breakthrough property, discovered independently by Hideki Shirakawa, Alan J. Heeger, and Alan G. MacDiarmid, revolutionized materials science by demonstrating that plastics could mimic the conductivity of metals, earning them the 2000 Nobel Prize in Chemistry.^[3] The discovery of polyacetylene's conductive potential in 1977 marked the birth of intrinsically conducting polymers, with doping dramatically increasing conductivity from ~10^-5 S/cm to metallic levels.^[4] Refinements in synthesis, such as precursor methods, improved material quality and enabled conductivities >20,000 S/cm, though air and moisture instability limited practical use.^[5] Undoped trans-polyacetylene features bond alternation (C–C ~1.44 Å, C=C ~1.36 Å) and a Peierls band gap of ~1.5 eV, with doping introducing delocalized charge carriers like solitons for conduction.^[6] Doped polyacetylene exhibits high electrical conductivity comparable to copper, alongside unique optical and magnetic properties. Its environmental instability has restricted it to research, but derivatives enhance solubility and stability. The polymer's significance lies in launching the era of conducting polymers, inspiring applications in organic electronics, batteries, sensors, and photovoltaics. While pristine polyacetylene remains niche, it enabled stable alternatives like polyaniline and polythiophenes for OLEDs and solar cells. As of 2024, ongoing research includes stabilized forms for green LEDs and energy storage.^[7]

Chemical Structure

Repeating Unit and Polymerization

Polyacetylene is an organic polymer with the chemical formula (CH)_n, where n denotes the degree of polymerization, consisting of a linear chain of carbon atoms alternately bonded to hydrogen atoms.^[8] The repeating unit is -CH=CH-, formed by the catalytic polymerization of acetylene (C_2H_2) monomers into a conjugated polyene backbone.^[8] The polymer exists in cis and trans isomeric forms, differing in the configuration around the double bonds along the chain. In the cis isomer, the hydrogen atoms on adjacent carbons are on the same side of the double bond, resulting in a more coiled structure, while the trans isomer has them on opposite sides, leading to a more extended, zigzag chain. Both configurations maintain a planar backbone due to the sp^2 hybridization of the carbon atoms, which maximizes π-orbital overlap in the conjugated system.^[8] Structural studies reveal alternating bond lengths characteristic of the conjugated diene units: the double bonds (C=C) measure approximately 1.35-1.37 Å, and the single bonds (C-C) approximately 1.44-1.46 Å, with slight variations between isomers—the cis form showing a more uniform double bond length of 1.37 Å, and the trans form exhibiting clearer alternation at 1.36 Å (double) and 1.44 Å (single).^[9] These dimensions contribute to the planarity and rigidity of the chain, as confirmed by NMR spectroscopy.^[9] In typical polyacetylene films, molecular weights range from 10,000 to 100,000 Da, corresponding to degrees of polymerization of approximately 400 to 4,000 repeating units, with higher values achieved under optimized conditions.^[8]

Conjugation and Electronic Configuration

Polyacetylene features a linear polymer chain composed of repeating -CH=CH- units, characterized by alternating single and double bonds that give rise to an extended conjugated π-system. This conjugation arises from the overlap of p_z atomic orbitals on adjacent sp²-hybridized carbon atoms, allowing π-electrons to delocalize across the chain and form a one-dimensional electronic structure. In the undoped state, this delocalization results in a band structure model with a filled valence band and an empty conduction band, separated by a HOMO-LUMO gap of approximately 1.8 eV, which corresponds to the optical band gap observed in trans-polyacetylene films.^[10]^[11] The band gap in trans-polyacetylene originates from a Peierls distortion, a lattice instability that doubles the unit cell and introduces bond alternation, stabilizing the system by lowering the total energy through the opening of a gap at the Brillouin zone boundary. This distortion transforms the otherwise metallic undimerized chain into a semiconductor, with the alternating bond lengths (short double bonds ~1.36 Å and long single bonds ~1.44 Å) enhancing electron-phonon coupling and preventing perfect delocalization. The Peierls mechanism is particularly pronounced in trans-polyacetylene due to its planar conformation, which maximizes π-overlap, unlike the twisted cis isomer.^[12] A simple quantum mechanical description of the π-electrons employs Hückel molecular orbital theory, treating the undimerized chain as a 1D tight-binding model with nearest-neighbor interactions. The energy dispersion relation for the π-band is given by

E_k = \alpha + 2\beta \cos(ka),

where k is the wave vector, a is the lattice constant (C-C distance ~1.4 Å), \alpha is the on-site Coulomb integral (typically set to 0 for energy reference), and \beta is the resonance integral (hopping parameter, ~ -2.5 to -3.5 eV). At half-filling, the Fermi level lies at the band center, and the Peierls distortion modulates the hopping parameters (\beta_1 \neq \beta_2) to open a gap of ~1.8 eV at k = \pi/(2a), consistent with experimental absorption onset.^[13]^[14]

History

Initial Discoveries

The first synthesis of polyacetylene was achieved by Giulio Natta and his collaborators in 1958 through the polymerization of acetylene using Ziegler-Natta catalysts, such as triethylaluminum combined with titanium compounds, which produced black, insoluble powders of low solubility and limited structural uniformity. These early materials were primarily of interest to organic chemists studying stereoregular polymers, but their powdery form and instability toward air and moisture restricted further exploration of their properties. In the 1960s, Japanese researchers, notably Sakuji Ikeda at the Tokyo Institute of Technology, advanced the field by examining the polymerization mechanisms and experimenting with film formation techniques, including thermal treatment of the resulting powders to enhance cohesion and structural order.^[15] Ikeda's group, which later included Hideki Shirakawa as a graduate student starting in 1966, focused on catalyst variations to better understand acetylene's conversion to polyacetylene, though these efforts still yielded brittle, non-uniform films prone to degradation.^[8] Their work laid the groundwork for improved material handling, but challenges such as inconsistent film thickness and sensitivity to environmental factors persisted.^[15] A serendipitous breakthrough occurred in October 1967, when a student in Shirakawa's group mistakenly used a Ziegler-Natta catalyst concentration about 1000 times higher than intended, resulting in the formation of a shiny, metallic-looking film of polyacetylene on the reaction vessel wall instead of the usual black powder. This "fortuitous error" prompted further investigation into high-catalyst methods for film synthesis.^[2] Entering the early 1970s, key obstacles included poor control over the cis-trans isomer distribution—typically favoring the less stable cis form at lower polymerization temperatures—and low molecular weights that resulted in mechanically weak polymers with degrees of polymerization often below 100. These issues complicated characterization and application, as the materials exhibited variable conjugation lengths and tended to degrade during processing.^[8] A pivotal advancement occurred in 1974, when Shirakawa, along with Tsutomu Ito and Ikeda, reported the synthesis of shiny, free-standing films of cis-rich polyacetylene (with up to 98% cis content) by polymerizing acetylene directly on the surface of a highly concentrated Ziegler-Natta catalyst solution, enabling the formation of coherent, metallic-luster sheets up to several micrometers thick. This method marked a significant improvement in material quality, facilitating subsequent spectroscopic and structural analyses that highlighted polyacetylene's conjugated backbone.

Development of Conductivity

In 1977, Hideki Shirakawa, visiting from the Tokyo Institute of Technology, collaborated with Alan G. MacDiarmid and Alan J. Heeger at the University of Pennsylvania to investigate the properties of polyacetylene films, which had been synthesized earlier through Ziegler-Natta polymerization but initially exhibited low conductivity on the order of 10^{-5} S/cm. During these experiments, the team exposed the silver-like films to halogen vapors, such as iodine, in an effort to explore potential chemical modifications; unexpectedly, this doping process dramatically enhanced the material's electrical conductivity by up to ten orders of magnitude, reaching values as high as 10^{5} S/cm, transforming the insulating polymer into a metallic conductor. This serendipitous observation, stemming from routine characterization of vapor-exposed samples, marked the birth of conductive polymers and demonstrated that charge transfer doping could induce delocalized charge carriers in conjugated systems.^[16]^[17] The breakthrough prompted rapid follow-up studies, confirming that iodine intercalation between polymer chains created a p-type dopant effect, enabling systematic control over conductivity levels. This work not only highlighted polyacetylene's potential as the first organic metal but also shifted paradigms in materials science, inspiring research into tunable electronic properties of organic materials. For their pioneering contributions to the discovery and development of conductive polymers, Shirakawa, MacDiarmid, and Heeger were awarded the 2000 Nobel Prize in Chemistry.^[18]^[16] In the early 1980s, advancements focused on improving the stability and processability of doped polyacetylene films, alongside theoretical frameworks to explain the underlying physics. Wu-Pei Su, John R. Schrieffer, and Alan J. Heeger developed the Su-Schrieffer-Heeger (SSH) model, a one-dimensional tight-binding Hamiltonian that incorporates electron-phonon coupling to describe bond alternation and soliton formation in trans-polyacetylene chains. This model elucidated how doping introduces mobile solitons as charge carriers, with formation energies lower than band-gap excitations, providing a quantum mechanical basis for the observed high conductivities and predicting key experimental signatures like gap states. These theoretical insights, combined with refined film preparation techniques yielding more uniform and air-stable samples, solidified polyacetylene's role as a benchmark for understanding conductivity in conjugated polymers.^[19]

Synthesis

Ziegler-Natta Polymerization

The Ziegler-Natta polymerization of acetylene represents a foundational coordination catalytic method for synthesizing polyacetylene, first demonstrated by Giulio Natta and coworkers in the mid-1950s using transition metal halide systems. This approach was later refined with alkoxide-based catalysts to produce higher-quality materials, enabling the formation of stereoregular polymers with extended conjugation. The technique relies on the activation of titanium compounds by organoaluminum cocatalysts to generate active sites capable of inserting acetylene monomers sequentially. The standard catalyst system consists of titanium(IV) butoxide, Ti(OBu)₄, combined with triethylaluminum, AlEt₃, at a molar ratio of approximately 1:4, which reduces the titanium to a lower oxidation state and forms alkylated active centers on the metal. These sites facilitate the polymerization through a coordination-insertion mechanism, wherein acetylene coordinates to the titanium center via its π-orbitals before undergoing migratory insertion into a metal-carbon bond, propagating the growing chain. Studies using nutation NMR have confirmed head-to-tail linkages and the absence of significant branching or cyclization in the resulting polymer.^[20]^[21] Polymerization conditions significantly influence the stereochemistry of the product: low temperatures around -78 °C promote the formation of cis-polyacetylene with high stereoregularity (up to 98% cis content), while room temperature (approximately 20 °C) or higher yields mixtures favoring the more stable trans isomer. The reaction is typically performed in an inert atmosphere, either in solution (e.g., toluene or pentane) or via gas-phase exposure of acetylene to a catalyst-coated surface, resulting in the deposition of metallic-looking films directly on the reactor walls due to the insolubility of the growing polymer. This method achieves high yields, often exceeding 90% conversion, and produces films with molecular weights in the range of 10⁴–10⁵ g/mol. However, it operates as a batch process with challenges in precisely controlling the cis/trans ratio and scaling up for continuous production.^[22]

Metathesis and Precursor Methods

Ring-opening metathesis polymerization (ROMP) of cyclooctatetraene (COT) represents a key metathesis-based approach to synthesizing polyacetylene, offering improved control over molecular weight and morphology compared to traditional methods. Post-2000 developments have leveraged advanced ruthenium-based Grubbs catalysts, such as the second-generation (G2) and third-generation (G3) variants, to facilitate living polymerization of COT, yielding highly conjugated polyacetylene with defined chain lengths. For instance, single-chain studies using G2 catalyst demonstrated precise control over polymerization dynamics, enabling the production of uniform polyacetylene segments for advanced materials research. More recently, in 2025, a novel metallacycle transfer strategy combined with G3-catalyzed ROMP of functionalized COT derivatives produced structurally unique polyacetylenes with molecular weights up to 144 kDa, enhancing processability and conjugation length.^[23] The precursor polymer route provides an alternative pathway to polyacetylene by first forming a soluble, non-conjugated polymer from acetylene derivatives, followed by thermal elimination to generate the conjugated (CH)_x structure. In the seminal Durham route, developed in the 1980s but refined in subsequent decades, a tricyclic precursor such as poly(7,8-bis(trifluoromethyl)tricyclo[4.2.2.0^2,5]deca-3,7,9-triene) is synthesized via ring-opening metathesis, cast into films, and then converted through symmetry-allowed thermal elimination at temperatures around 300–400 °C, releasing 1,2-bis(trifluoromethyl)benzene as a byproduct. This method circumvents the insolubility and heterogeneity of direct polymerization, allowing purification and orientation of the precursor prior to conversion. The Durham approach remains widely adopted for its ability to yield uniform films without catalyst residues.^[17]^[24] Recent advancements from 2020 to 2025 have focused on organometallic catalysis to synthesize substituted polyacetylenes with enhanced solubility, addressing longstanding challenges in processability. Rhodium-based catalysts, particularly [Rh(nbd)(dppe)]⁺ complexes, enable living polymerization of bulky monosubstituted acetylenes, producing helical polymers soluble in common organic solvents like THF and chloroform. These catalysts achieve high stereoregularity and narrow polydispersity (PDI < 1.2), with substitutions such as phenothiazinyl or aryl groups conferring solubility while maintaining conjugation. Tungsten and molybdenum carbene complexes have also been optimized for di- and tri-substituted acetylenes, yielding polymers with up to 100% cis-content for optical applications. Such innovations have expanded the scope to functional materials, with over 200 new derivatives reported in high-impact reviews.^[25]^[26] These methods typically achieve high yields and purity, with conversions up to 90% in thermal elimination steps, facilitating the production of oriented films through precursor stretching. For example, Durham-route precursors can be drawn to draw ratios exceeding 4:1 before elimination, resulting in highly aligned polyacetylene chains with improved electrical anisotropy. ROMP approaches similarly yield >85% polymer with minimal defects, as confirmed by NMR and GPC analyses, enabling defect-free films for device integration.^[27]

Doping

Doping Processes

Doping of polyacetylene involves the introduction of chemical or electrochemical agents to modify its electronic properties by creating charge carriers. Chemical doping is typically performed by exposing polyacetylene films to vapors or solutions of dopants at room temperature, allowing controlled incorporation into the polymer matrix. P-type doping, or oxidation, removes electrons from the polyacetylene chain, generating positive charge carriers. Common oxidants include iodine (I₂), arsenic pentafluoride (AsF₅), and ferric chloride (FeCl₃). For instance, exposure to I₂ vapor leads to the formation of polyiodide counterions such as I₃⁻, with the reaction often represented as (CH)_x + \frac{3y}{2} I_2 \rightarrow [(CH)^{y+}(I_3^-)_y]_x where the dopant level y (typically 0.1-0.2) corresponds to the fraction of oxidized carbon atoms.^[8] FeCl₃ doping is achieved by immersing films in nitromethane solutions or exposing them to the vapor of solid FeCl₃, resulting in the incorporation of FeCl₄⁻ anions for charge balance. AsF₅ doping similarly uses vapor-phase exposure, producing AsF₆⁻ counterions. Dopant levels are generally maintained at 1-10 mol% to achieve optimal charge carrier density without excessive structural disruption. N-type doping, or reduction, adds electrons to the polymer, creating negative charge carriers. Reductants such as sodium (Na) or other alkali metals are employed, typically by immersing polyacetylene films in solutions containing the metal, like sodium-naphthalene in tetrahydrofuran, which facilitates electron transfer and insertion of metal cations as counterions.^[8] Electrochemical doping offers precise control over dopant incorporation by using polyacetylene films as working electrodes in an electrolyte solution, such as LiClO₄ in acetonitrile. P-type doping occurs via anodic oxidation, where anions from the electrolyte (e.g., ClO₄⁻) are inserted into the polymer to balance the positive charges generated, following the general scheme [CH]_x + y A^- \rightarrow [CH^+(A^-)_y]_x. Conversely, n-type doping is achieved through cathodic reduction, incorporating cations (e.g., Li⁺) to compensate for the added electrons. This method allows reversible doping and undoping, with dopant levels adjustable by applied potential and charge passed.

Charge Carrier Formation

Upon doping, polyacetylene undergoes structural and electronic modifications that generate charge carriers, primarily through the introduction of dopants that abstract or donate electrons, leading to localized defects in the polymer chain.^[28] In trans-polyacetylene, these charge carriers manifest as solitons, which serve as efficient charge storage units. Solitons are topological defects representing domain walls where the alternating single and double bond orders of the dimerized chain reverse phase, creating a localized region of bond alternation mismatch that spans approximately 10-15 carbon atoms.^[29] Neutral solitons carry spin-1/2 and are non-magnetic in pairs, while charged solitons (positive or negative) are spinless and introduce mid-gap electronic states that accommodate the dopant-induced charges without significant energy penalty, enabling high conductivity.^[28] In contrast, cis-polyacetylene or heavily doped trans configurations favor polarons and bipolarons as charge carriers. A polaron consists of a charge coupled to a lattice distortion over a shorter range than a soliton, forming a self-trapped state with two levels in the band gap; bipolarons involve two charges on adjacent sites with enhanced lattice relaxation. The polaron binding energy, representing the stabilization from this electron-lattice coupling, is approximately 0.05-0.1 eV.^[30]^[31] The Su-Schrieffer-Heeger (SSH) model, originally formulated for undoped polyacetylene, extends to doped systems by incorporating charge defects that populate a narrow band of soliton or polaron states at mid-gap, partially filling the valence or conduction bands. This band filling reduces the effective Peierls gap from ~1.8 eV in the pristine state, narrowing it progressively with increasing dopant concentration and fostering metallic-like behavior through overlap of defect states with the band edges.^[29]^[30] Experimental confirmation of these mid-gap states comes from electron spin resonance (ESR) spectroscopy, which detects unpaired spins from neutral solitons with a narrow linewidth indicative of delocalization, and from optical absorption measurements revealing characteristic sub-gap transitions around 0.7-1.5 eV attributed to soliton or polaron excitations.^[32]^[33]^[34]

Properties

Electrical Conductivity

Undoped polyacetylene is an electrical insulator with a conductivity on the order of $10^{-10} S/cm for the cis isomer, reflecting its wide band gap of approximately 1.7 eV.^[17] Heavy doping with oxidants such as iodine or AsF_5 introduces charge carriers, dramatically enhancing conductivity to values exceeding $10^5 S/cm in optimized samples, which is comparable to that of copper at $5.96 \times 10^5 S/cm.^[35] This transformation from insulator to conductor spans over ten orders of magnitude, establishing polyacetylene as a prototypical conducting polymer.^[36] In stretched films, the electrical conductivity of doped polyacetylene exhibits strong anisotropy, with intrachain transport along the alignment direction yielding values 10 to 100 times higher than perpendicular to the chains.^[17] This directional preference arises from the enhanced mobility of charge carriers parallel to the conjugated \pi-electron backbone, while interchain hopping limits perpendicular conduction.^[37] The temperature dependence of conductivity in heavily doped polyacetylene reveals a metallic regime above approximately 100 K, where \sigma decreases weakly and nearly linearly with falling temperature, indicative of delocalized carriers in a disordered one-dimensional system.^[38] At lower temperatures, transport shifts to variable range hopping between localized states, following \sigma \propto \exp[-(T_0/T)^{1/2}] or similar forms due to disorder effects.^[36] Key factors influencing conductivity include the dopant species, which determines carrier concentration and mobility—as seen in higher values with AsF_5 versus iodine—and polymer orientation from stretching, which minimizes defects and aligns chains for efficient transport.^[5] Defect density, arising from synthesis imperfections or environmental exposure, further modulates performance by scattering carriers and localizing states.^[39]

Optical and Mechanical Traits

Polyacetylene's optical properties stem from its extended π-conjugation along the polymer backbone, leading to distinct absorption characteristics. In the undoped form, primarily trans-polyacetylene, the material features a prominent π-π* transition at approximately 1.8 eV, which defines its optical bandgap and results in absorption primarily in the visible to near-ultraviolet range. This transition arises from electronic excitations between the valence and conduction bands in the one-dimensional Peierls-distorted lattice. Upon doping with oxidants or reductants, the bandgap effectively closes, and the absorption spectrum broadens with a Drude-like free carrier tail extending into the infrared region, reflecting increased metallic conductivity and intraband transitions. The refractive index of polyacetylene, typically around 2.0 in the visible spectrum, contributes to its potential in optical devices, such as waveguides or lenses, where high-index materials are advantageous for light confinement. This value, derived from spectral analysis of thin films, varies slightly with isomerism—higher for cis configurations—and wavelength, peaking near absorption bands due to anomalous dispersion.^[40] Mechanically, undoped polyacetylene films exhibit a Young's modulus of 5–10 GPa and tensile strength up to 100 MPa, properties influenced by the inherent flexibility of the linear polymer chains and interchain interactions via van der Waals forces.^[41] These values position polyacetylene as moderately stiff yet elastic compared to other conjugated polymers, with elongation at break often exceeding 4% before fracture, enabling applications requiring bendability.^[42] Chain flexibility allows for reversible deformation, though brittleness in the trans isomer limits overall ductility without processing aids. Orientation induced by mechanical stretching dramatically enhances mechanical performance, particularly along the draw direction, where the Young's modulus can increase to 40–50 GPa due to alignment of the fibrillar microstructure and improved load transfer between chains.^[41] This anisotropy arises from the unidirectional extension of the conjugated backbone, reducing transverse modulus while boosting axial tensile properties, as observed in films drawn to ratios of 7–15.^[43] Such oriented structures mimic high-performance fibers, though doping typically reduces these moduli by 4–5 times through weakened interchain cohesion.^[41]

Stability Issues

Polyacetylene, especially in its doped form, is highly sensitive to air exposure, where oxidation by molecular oxygen (O₂) promotes chain scission along the polymer backbone, leading to a rapid loss of electrical conductivity within hours. This degradation disrupts the extended conjugation necessary for charge transport, forming oxygen-containing defects such as carbonyl groups that shorten the effective π-electron delocalization length. Undoped polyacetylene shows a more gradual decline, with conductivity decreasing by approximately one order of magnitude over 1000 hours in ambient conditions, but doped variants degrade far more quickly due to enhanced reactivity of the charged carriers.^[44]^[45]^[46] Moisture further exacerbates instability through the hydrolysis of dopants, particularly p-type dopants like AlCl₄⁻, which react to produce carbonyl defects with adjacent sp³-hybridized CH₂ groups and carbinol-type structures via tautomeric equilibrium. These reactions introduce irreversible structural disorder, breaking conjugation and significantly lowering direct-current conductivity even after subsequent redoping attempts. As a result, polyacetylene processing and storage necessitate strictly inert atmospheres, such as argon or nitrogen, to avert hydrolytic breakdown and maintain material integrity.^[47]^[47] Thermally, polyacetylene exhibits limited stability, with decomposition initiating above 200°C as dopant loss and backbone fragmentation occur, particularly in oxidative environments. Ultraviolet (UV) exposure compounds this vulnerability by inducing crosslinking reactions that rigidify the polymer structure, reduce flexibility, and impair electrical performance through morphological changes and defect formation. Both cis and trans isomers share this susceptibility, though substituted variants may offer marginal improvements.^[48] Encapsulation methods, such as coating with glass or polymer barriers, slow oxygen ingress and extend operational lifetimes by orders of magnitude compared to bare films.^[44] Recent advancements as of 2025 in substituted derivatives, including those bearing trialkylsilyl groups like poly{1-[4-(trimethylsilyl)phenyl]-2-phenylacetylene}, provide inherent air resistance by sterically hindering oxidative attack on the backbone, enabling stable performance in ambient conditions for electronics applications. These modifications, often combined with nanoparticle nanocomposites (e.g., SiO₂ or ZnO), have demonstrated enhanced durability, with minimal degradation over extended operation in doped states.^[49]

Applications

Established Uses

In the 1980s, polyacetylene emerged as a promising material for rechargeable battery prototypes, particularly as cathodes or anodes in lithium cells, leveraging its ability to undergo reversible doping to store and release charge efficiently.^[50] For instance, reduced polyacetylene (Li_y CH)_x served as a lightweight anode in non-aqueous lithium batteries, demonstrating stable voltages and high coulombic efficiency in early electrochemical tests.^[51] This high electrical conductivity, reaching up to 10^3 S/cm when doped, enabled polyacetylene to function as a "plastic metal" in these energy storage devices.^[52] Polyacetylene's reversible doping-dedoping process also found application in early sensors for detecting gases and chemicals, where changes in conductivity upon exposure to analytes allowed for sensitive, room-temperature detection.^[53] As the prototype conducting polymer, it was explored for chemiresistive gas sensors targeting toxic vapors and volatile organic compounds, with doping reversibility providing rapid response and recovery.^[54] Additionally, doped polyacetylene was prototyped for antistatic coatings and electromagnetic interference (EMI) shielding films, capitalizing on its metallic-like conductivity to dissipate static charges and absorb microwaves.^[55] These applications included corrosion-inhibiting layers on printed circuit boards and radar-absorbing materials for stealth technology, where thin films provided effective shielding without adding significant weight.^[55] Despite these innovations, polyacetylene's commercial adoption was severely limited by its chemical instability, particularly rapid degradation in air and moisture, which caused conductivity loss and device failure over time.^[52] As a result, it was largely supplanted by more stable conducting polymers like polyaniline, which offer better environmental resistance and processability for practical implementations.^[52]

Recent Developments

In 2024, polyacetylene was used in the development of green light-emitting diodes (LEDs) with nanoparticle fillers such as SiO₂ and ZnO, demonstrating improved luminescence efficiency up to 182 cd/m² and operational stability up to 90 minutes. These diodes exhibited a peak emission at 545 nm.^[7] Computational studies in 2025 highlighted polyacetylene's potential in energy applications, particularly for CO2 capture using voltage-doped films. Density functional theory simulations revealed that applying a negative voltage to polyacetylene cathodes facilitates direct carboxylation of the polymer by CO2 molecules, with electron densities up to -0.04 e per carbon atom lowering activation barriers to below 1 eV and enabling spontaneous desorption for recyclability. This process operates under ambient conditions, offering a thermodynamically favorable route for electrochemical carbon sequestration without additional energy inputs for regeneration.^[56] Aligned polyacetylene nanofibers have shown exceptional thermal conductivity in modeling studies, with density functional theory-informed simulations predicting values up to 480 W/mK along the chain direction at room temperature. These predictions, derived from united-atom force fields parameterized for single chains and crystalline assemblies, underscore polyacetylene's superiority over conventional polymers like polyethylene, where alignment extends phonon mean free paths significantly. Such properties position aligned polyacetylene derivatives as candidates for thermal management in high-performance electronics.^[57] Market projections for conductive polymers forecast growth from USD 5.08 billion in 2023 to USD 9.03 billion by 2030, driven by demand in energy storage and wearable sensing technologies.^[58]

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... stretching, polyacetylene also exhibits a large anisotropy in its conduc- tivity due to the increased mobility of electrons along the oriented polymer ...
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The characterizations confirm the film has a poor toughness, whose elongation at break is about 4.47% and its tensile strength is about 36 MPa, as shown in ...<|separator|>
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cis-polyacetylene (CH)~ is a potentially valuable organic conductor, with conductivities 4 of up to l0 s S cm -1. However, its usefulness is limited by poor ...
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Sep 29, 2020 · In this work, we use first-principles density functional theory (DFT) calculations to parameterize a united-atom force field for polyacetylene ( ...Missing: nanofibers 2023 ~3000 W/ mK
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The ability to manipulate PA's conductivity through doping processes allows researchers to tailor its electrical characteristics for specific applications, ...
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The global conductive polymers market size was estimated at USD 5.08 billion in 2023 and is projected to reach USD 9.03 billion by 2030, growing at a CAGR ...Missing: polyacetylene hybrids