Polyacetylene discovery

The discovery of junipal focused the attention of Sorensen, who had been investigating the occurrence of polyacetylenes in Com-positae, on the possibility that these acetylenes were accompanied by thiophenes. From Coreopsis grandiflora Hogg ex sweet, 2-phenyl 5-(1-propynyl) thiophene (240) was isolated and its structure confirmed by synthesis of the tetrahydro compound, 2-phenyl-5-n-propyl-thiophene. From the root of tansy, the cis and trans isomers of methyl 5-(l-propynyl)-2-thienylacrylate (241) have been isolated. The total synthesis of trans (241) was achieved by reacting junipal with methylcarbethoxy triphenylphosphonium bromide (Wittig reaction) Several monosubstituted thiophenes, (242), (243), and... 

Polymer Batteries The discovery that doping of polyacetylene produced a highly conducting material was followed swiftly by the realization that this material was a rechargeable battery material which, optimistically, might lead to lightweight... 

Shirakawa, H., The discovery of polyacetylene film the dawning of an era of conducting polymers, Nobel lecture, December 8, 2000. 

A second major event in the saga of polymer conductors was the discovery that the doping processes of polyacetylene could be promoted and driven electrochemically in a reversible fashion by polarising the polymer film electrode in a suitable electrochemical cell (MacDiarmid and Maxfield, 1987). Typically, a three-electrode cell, containing the (CH) film as the working electrode, a suitable electrolyte (e.g. a non-aqueous solution of lithium perchlorate in propylene carbonate, here abbreviated to LiC104-PC) and suitable counter (e.g. lithium metal) and reference (e.g. again Li) electrodes, can be used. 

Since the discovery of doped polyacetylene, a range of polymer-intense semiconductor devices have been studied including normal transistors and field-effect transistors (FETs), and photodiodes and light-emitting diodes (LEDs). Like conductive polymers, these materials obtain their properties due to their electronic nature, specifically the presence of conjugated pi-bonding systems. 

In 1958, Natta and co-workers polymerized acetylene for the first time by using a Ti-based catalyst. This polymerization proceeds by the insertion mechanism like the polymerization of olefins. Because of the lack of processability and stability, early studies on polyacetylenes were motivated by only theoretical and spectroscopic interests. Thereafter, the discovery of the metallic conductivity of doped polyacetylene in 1977 stimulated research into the chemistry of polyacetylene, and now poly acetylene is recognized as one of the most important conjugated polymers. Many publications are now available about the chemistry and physics of polyacetylene itself. 

In the late 1970s Heeger and MacDiarmid found that polyacetylene [(CH)n] produced by Shirikawa s method exhibited a 12 order of magnitude increase in electrical conductivity when exposed to oxidizing agents. Since that discovery, a vast array of other CPs have been synthesized. The most common of these, in addition to polyacetylene, are shown below in Scheme 1. 

Before 1985, six crystalline forms of carbon were known two forms of graphite, two forms of diamond, and chaoit and carbon (VI) discovered in 1968 and 1972, respectively. In addition a number of almost pure amorphous forms exist, such as polyacetylene (7.60) and cumulene (7.61) and recently a number of interesting nanostructured forms of carbon have been produced (Section 15.8). The year 1985 marked the discovery of the fullerenes, which represent the only truly pure molecular form of carbon, are produced under very extreme conditions as carbon vapour condenses in an atmosphere of an inert gas such as helium. Harold Kroto s interest in this chemistry originated with microwave spectroscopic studies of the atmosphere of stars and interstellar dust clouds. Kroto wanted to try to reproduce in the laboratory spectra of carbon... 

The search for new organic metals and superconductors has attracted a great deal of attention in synthetic chemistry and material science since the discovery of high electrical conductivity in conjugated polymers such as polyacetylene [1], Lots of theoretical studies have been carried out in order to understand the mechanism of conductivity and superconductivity in the conjugated polymers and related... 

The recent interest in electroactive polymers started with the preparation of polyacetylene (CH) film [4] and the discovery of the exceptional electrical... 

The question of whether the bond lengths were equal or alternated in an infinite f-PAc chain was first answered satisfactorily using a Huckel model nearly twenty years before the discovery of metallic behaviour in PAc (Longuet-Higgins and Salem, 1959). This work was carried out at a time when the Huckel model was being used to model the evolution of the optical spectra of the polyenes, i.e. polyacetylene oligomers, as the length of the molecules increased. 

Shortly after the initial discovery of doping and the metal-insulator transition in polyacetylene, a theoretical description of the electronic structure was... 

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