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Live-cell Raman imaging based on bioorthogonal Raman probes with distinct signals in the cellular Raman-silent region (1800–2800 cm −1 ) has attracted great interest in recent years. We report here a class of water-soluble and biocompatible polydiacetylenes with intrinsic ultrastrong alkyne Raman signals that locate in this region for organelle-targeting live-cell Raman imaging. Using a host-guest topochemical polymerization strategy, we have synthesized a water-soluble and functionalizable master polydiacetylene, namely poly(deca-4,6-diynedioic acid) (PDDA), which possesses significantly enhanced (up to ~10 4 fold) alkyne vibration compared to conventional alkyne Raman probes. In addition, PDDA can be used as a general platform for multi-functional ultrastrong Raman probes. We achieve high quality live-cell stimulated Raman scattering imaging on the basis of modified PDDA. The polydiacetylene-based Raman probes represent ultrastrong intrinsic Raman imaging agents in the Raman-silent region (without any Raman enhancer), and the flexible functionalization of this material holds great promise for its potential diverse applications. Raman probes which operate in the cellular silent region are of interest for live cell imaging. Here, the authors report on the development of a water soluble polydiacetylene Raman probe with enhanced Raman signal in the silent region which can be functionalised for organelle targeting and demonstrate application.

In this work, the practical/analytical potential of an L‐valine‐derived polyacetylene (PLA) lyotropic liquid crystal (LLC) is examined to spectrally discriminate enantiomers (racemic mixture) or enantiotopic directions of a large collection (23) of (pro)chiral model compounds (from rigid to flexible and polar to apolar ones), thus covering various important aspects of enantiomorphism. Experimental 2 H‐ 1 H (deuterated analytes and at natural abundance level) and 13 C‐ 1 H NMR results are discussed in terms of the difference of 2 H‐RQCs or 13 C‐RCSAs and compared to those obtained in polypeptide‐type LLCs (PBLG). The analysis of the NMR results provides an overview of the enantiodifferentiation capabilities of PLA and gives useful/practical hints for the chemist to select the most appropriate chiral oriented system. Astonishing NAD NMR results were obtained in the case of one of the simplest, chiral alkanes, 3‐methylhexane. From a theoretical viewpoint, the data collected highlight the key molecular factors involved in orientation/discrimination processes, as a basis for optimizing computational prediction (molecular dynamics simulation), as well as designing novel helically chiral polymers as new enantiodiscriminating aligning media. In addition, a new, robust and efficient protocol to synthesize PLA and its enantiomer (PDA) on a large scale and with small polydispersities is proposed.

Hydrochromic materials have been actively investigated in the context of humidity sensing and measuring water contents in organic solvents. Here we report a sensor system that undergoes a brilliant blue-to-red colour transition as well as ‘Turn-On’ fluorescence upon exposure to water. Introduction of a hygroscopic element into a supramolecularly assembled polydiacetylene results in a hydrochromic conjugated polymer that is rapidly responsive (<20 μs), spin-coatable and inkjet-compatible. Importantly, the hydrochromic sensor is found to be suitable for mapping human sweat pores. The exceedingly small quantities (sub-nanolitre) of water secreted from sweat pores are sufficient to promote an instantaneous colorimetric transition of the polymer. As a result, the sensor can be used to construct a precise map of active sweat pores on fingertips. The sensor technology, developed in this study, has the potential of serving as new method for fingerprint analysis and for the clinical diagnosis of malfunctioning sweat pores. Materials capable of colour changes in response to stimuli are useful in sensors and other applications. Here the authors show a conjugated polymer that rapidly responds to the presence of water, and use it as a sensor to map active sweat pores as a means of fingerprint analysis.

In the chromatographic separation of enantiomers the order of elution is determined by the strength of diasteromeric interactions between the components of the mixture and a chiral stationary phase. For analytical purposes, it is ideal to have the minor component elute first, whereas in the preparative mode a faster elution of the major component is desirable. Here we describe a stationary phase constructed from a polyacetylene that bears 2,2′-bisphenol-derived side chains in which chirality can be switched in the solid state prior to use. Both the macromolecular helicity of the polymer backbone and the axial chirality of the side chains can be switched in the solid state by interaction with a chiral alcohol, but importantly are maintained after removal of the chiral alcohol because of a memory effect. The chiral stationary phase thus prepared was used to separate the enantiomers of trans -stilbene oxide with the enantiomer elution order determined by the preseparation treatment. Reversible chirality switching and memory is demonstrated in a helical polyacetylene. Both the helicity of the polymer backbone and the axial chirality of the side chains contribute to the memory effect. When used to produce a chiral stationary phase for a chromatographic enantiomer resolution it was possible to switch the elution order under identical chromatographic conditions.

Since the discovery of conductive polyacetylene, conductive electroactive polymers are at the focal point of technology generation and biocommunication materials. The reasons why this research never stops growing, are twofold: first, the demands from the advanced technology towards more sophistication, precision, durability, processability and cost-effectiveness; and second, the shaping of conducting polymer research in accordance with the above demand. One of the major challenges in conducting polymer research is addressing the processability issue without sacrificing the electroactive properties. Therefore, new synthetic designs and use of post-modification techniques become crucial than ever. This quest is not only advancing the field but also giving birth of new hybrid materials integrating merits of multiple functional motifs. The present review article is an attempt to discuss the recent progress in conducting polymer grafting, which is not entirely new, but relatively lesser developed area for this class of polymers to fine-tune their physicochemical properties. Apart from conventional covalent grafting techniques, non-covalent approach, which is relatively new but has worth creation potential, will also be discussed. The aim is to bring together novel molecular designs and strategies to stimulate the existing conducting polymer synthesis methodologies in order to enrich its fascinating chemistry dedicated toward real-life applications.

Polymer mechanochemistry has traditionally been employed to study the effects of mechanical force on chemical bonds within a polymer backbone or to generate force-responsive materials. It is under-exploited for the scalable synthesis of wholly new materials by chemically transforming the polymers, especially products inaccessible by other means. Here we utilize polymer mechanochemistry to synthesize a fluorinated polyacetylene, a long-sought-after air-stable polyacetylene that has eluded synthesis by conventional means. We construct the monomer in four chemical steps on gram scale, which involves a rapid incorporation of fluorine atoms in an exotic photochemical cascade whose mechanism and exquisite stereoselectivity were informed by computation. After polymerization, force activation by ultrasonication produces a gold-coloured, semiconducting fluoropolymer. This work demonstrates that polymer mechanochemistry is a valuable synthetic tool for accessing materials on a preparative scale.Fluorinated polyacetylene has typically proven to be inaccessible using traditional polymer synthesis, but there is much interest in its predicted properties. Now, a mechanochemical unzipping strategy has succeeded in the synthesis of a gold-coloured, semiconducting fluorinated polyacetylene with improved stability in air compared to polyacetylene.

Here we demonstrate the synthesis of cyclic polyacetylene (c-PA), or [∞]annulene, via homogeneous tungsten-catalysed polymerization of acetylene. Unique to the cyclic structure and evidence for its topology, the c-PA contains >99% trans double bonds, even when synthesized at −94 °C. High activity with low catalyst loadings allows for the synthesis of temporarily soluble c-PA, thus opening the opportunity to derivatize the polymer in solution. Absolute evidence for the cyclic topology comes from atomic force microscopy images of bottlebrush derivatives generated from soluble c-PA. Now available in its cyclic form, initial characterization studies are presented to elucidate the topological differences compared with traditionally synthesized linear polyacetylene. One advantage to the synthesis of c-PA is the direct synthesis of the trans–transoid isomer. Low defect concentrations, low soliton concentration, and relatively high conjugation lengths are characteristics of c-PA. Efficient catalysis permits the rapid synthesis of lustrous flexible thin films of c-PA, and when doped with I2, they are highly conductive (398 (±76) Ω−1 cm−1).Lustrous flexible thin films of semiconducting cyclic polyacetylene (c-PA) have been synthesized and characterized. Rapid and efficient tungsten-catalysed acetylene polymerization conditions produce temporarily soluble c-PA, enabling the in situ derivatization of this typically insoluble polymer. Compelling evidence for the cyclic topology—and its influence on the physical properties of the polymer—are presented.

Two types of disubstituted polyacetylenes were synthesized and these polyacetylenes exhibited both liquid crystallinity and luminescence. First, a simple disubstituted polyacetylene with short alkyl chains was synthesized by one-step reaction. The disubstituted polyacetylene derivative showed high molecular weight and high crystallinity. Next, a disubstituted polyacetylene derivative having long alkyl chains with photo-cross-linking of liquid crystal domains under visible light was prepared via multi-step reaction. Both the polymers showed good solubility. The polymers exhibited lyotropic liquid crystallinity, a smectic phase, and liquid crystal concentration chromism as a function of color change depends on concentration in solution. The polymers were oriented under a magnetic field. Characterization of the disubstituted polyacetylenes was carried out with nuclear magnetic resonance spectroscopy, gel permeation chromatography, infrared spectroscopy, UV–vis absorption spectroscopy, fluorescence spectroscopy, and polarizing optical microscopy observations. Magnetic orientation in evaporation process via formation of lyotropic liquid crystal for obtaining uniaxial domain structure was performed.

Polymeric semiconductors have rapidly evolved from early conductive polymers, such as polyacetylene, to high-performance donor-acceptor copolymers, offering a unique combination of mechanical flexibility, solution processability, and tunable optoelectronic properties. These advancements have positioned polymeric semiconductors as versatile materials for next-generation electronics, including wearable, stretchable, and bio-integrated devices, IoT systems, and soft robotics. In this review, we systematically present the fundamental principles of polymeric semiconductors, including electronic structure, charge transport mechanisms, molecular packing, and solid-state morphology, and elucidate how these factors collectively govern device performance. We further discuss recent advances in synthesis strategies, thin-film processing techniques, molecular doping, and interface engineering, emphasizing their critical roles in improving operational stability, charge-carrier mobility, and energy efficiency. Key applications-such as organic photovoltaics, field-effect transistors, neuromorphic devices, and memristors-are analyzed, with a focus on the intricate structure-property-performance relationships that dictate functionality. Finally, we highlight emerging directions and scientific innovations, including sustainable and degradable polymers, hybrid and two-dimensional polymer systems, and novel strategies to enhance device stability and performance. By integrating fundamental polymer science with device engineering, this review provides a comprehensive, structured, and forward-looking perspective, identifying knowledge gaps and offering insights to guide future breakthroughs and the rational design of high-performance, multifunctional, and environmentally responsible polymeric electronic devices.

Recent developments in the synthesis of substituted polyacetylenes have considerably benefitted from advancements in organometallic catalysis; however, most important developments rely on the advent of Rh-catalyzed living polymerizations. The latter not only allow the tailoring of well-defined degrees of polymerization with low and narrow polydispersity but also enable access to stereochemical well-defined cis-transoidal polymers with a helical structure. These novel polymers open new avenues for application in photonics and electronics. Rh-catalyzed living polymerizations are mild and concise metal-catalyzed polymer syntheses that not only allow for the decoration of sidechains with multiple functionalities, including chiral units, but also enable enantioselective induction of helical chirality, memory of chirality, well-defined copolymerization, and end-group functionalization at both termini. This review summarizes recent developments in metal-catalyzed syntheses of substituted polyacetylenes, with a special focus on Rh-catalyzed living polymerizations.