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Bechgaard Salt
In organic chemistry, a Bechgaard salt is any one of a number of organic charge-transfer complexes that exhibit superconductivity at low temperatures. They are named for chemist Klaus Bechgaard, who was one of the first scientists to synthesize them and demonstrate their superconductivity with the help of physicist Denis Jérome. Most Bechgaard salt superconductors are extremely low temperature, and lose superconductivity above the 1–2 K range, although the most successful compound in this class superconducts up to almost 12 K. All Bechgaard salts are formed using a small, planar organic molecule as an electron donor, with any of a number of electron acceptors (such as perchlorate, , or tetracyanoethylene, TCNE). All the organic electron donors contain multiply conjugated heterocycles with a number of properties, including planarity, low ionization potential and good orbital overlap between heteroatoms in neighboring donor molecules. These properties help the ...
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Tetrathiafulvalene
Tetrathiafulvalene is an organosulfur compound with the formula (. Studies on this heterocyclic compound contributed to the development of molecular electronics. TTF is related to the hydrocarbon fulvalene, , by replacement of four CH groups with sulfur atoms. Over 10,000 scientific publications discuss TTF and its derivatives. Preparation The high level of interest in TTFs has spawned the development of many syntheses of TTF and its analogues. Most preparations entail the coupling of cyclic building blocks such as 1,3-dithiole-2-thion or the related 1,3-dithiole-2-ones. For TTF itself, the synthesis begins with the trithiocarbonate , which is S-methylated and then reduced to give , which is treated as follows: :H2C2S2CH(SCH3) + HBF4 -> 2C2S2CH+F4- + HSCH3 :2 2C2S2CH+F4- + 2 Et3N -> (H2C2S2C)2 + 2 Et3NHBF4 Redox properties Bulk TTF itself has unremarkable electrical properties. Distinctive properties are, however, associated with salts of its oxidized derivatives, suc ...
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Organic Chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; Greeves, N. and Warren, S. (2012) ''Organic Chemistry''. Oxford University Press. pp. 1–15. . Study of structure determines their structural formula. Study of properties includes physical and chemical properties, and evaluation of chemical reactivity to understand their behavior. The study of organic reactions includes the chemical synthesis of natural products, drugs, and polymers, and study of individual organic molecules in the laboratory and via theoretical ( in silico) study. The range of chemicals studied in organic chemistry includes hydrocarbons (compounds containing only carbon and hydrogen) as well as compounds based on carbon, but also containing other elements, especially oxygen, nitrogen, sulfur, phosphorus (included in ...
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Charge-transfer Complex
In chemistry, a charge-transfer (CT) complex or electron-donor-acceptor complex describes a type of supramolecular assembly of two or more molecules or ions. The assembly consists of two molecules that self-attract through electrostatic forces, i.e., one has at least partial negative charge and the partner has partial positive charge, referred to respectively as the electron acceptor and electron donor. In some cases, the degree of charge transfer is "complete", such that the CT complex can be classified as a salt. In other cases, the charge-transfer association is weak, and the interaction can be disrupted easily by polar solvents. Examples Electron donor-acceptor complexes A number of organic compounds form charge-transfer complex, which are often described as electron-donor-acceptor complexes (EDA complexes). Typical acceptors are nitrobenzenes or tetracyanoethylene. The strength of their interaction with electron donors correlates with the ionization potentials of the ...
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Superconductivity
Superconductivity is a set of physical properties observed in certain materials where electrical resistance vanishes and magnetic flux fields are expelled from the material. Any material exhibiting these properties is a superconductor. Unlike an ordinary metallic conductor, whose resistance decreases gradually as its temperature is lowered even down to near absolute zero, a superconductor has a characteristic critical temperature below which the resistance drops abruptly to zero. An electric current through a loop of superconducting wire can persist indefinitely with no power source. The superconductivity phenomenon was discovered in 1911 by Dutch physicist Heike Kamerlingh Onnes. Like ferromagnetism and atomic spectral lines, superconductivity is a phenomenon which can only be explained by quantum mechanics. It is characterized by the Meissner effect, the complete ejection of magnetic field lines from the interior of the superconductor during its transitions into the sup ...
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Klaus Bechgaard
Klaus Bechgaard (5 March 1945 – 7 March 2017) was a Danish scientist and chemist, noted for being one of the first scientists in the world to synthesize a number of organic charge transfer complexes and demonstrate their superconductivity, therefore the name Bechgaard salt. These salts all exhibit superconductivity at low temperatures. The first unconventional superconductor composed of organic material, was discovered by Bechgaard and Denis Jerome in 1979. This discovery garnered attention in the international scientific community, and for a period he was one of the most cited scientists in the field of natural sciences. He also received a nomination for the Nobel Prize in chemistry for this discovery. Research Klaus Bechgaard did research at the University of Copenhagen, where he also held a Professorship in organic chemistry until 1993. From 1993 until 2000 he was the chairman of the Department of Physics and Chemistry at Risø and in 2001 he was appointed head of the ne ...
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Denis Jérome
Denis Jerome (born 28 February 1939 in Paris) is a French experimental physicist in the field of condensed matter, who contributed to the discovery of superconductivity in organic conductive matter. Career He studied at the Sorbonne, where he obtained his bachelor's degree in science in 1960, then the diploma of advanced studies in solid-state physics. In 1965, he obtained his doctorate in science under the supervision of Professor Anatole Abragam at the University of Paris-Saclay. From 1965 to 1966, he worked as a post-doctoral fellow at the University of California at San Diego, in the laboratory of Professor Walter Kohn, winner of the 1998 Nobel Prize in Chemistry, where he conducted research in collaboration with Professor T. M. Rice. He then continued his post-doctoral research at Harvard University until March 1967. In October 1962, he joined the Centre national de recherche scientifique (CNRS) as a research intern. He successively became a research master in 1970, resea ...
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Electron Donor
In chemistry, an electron donor is a chemical entity that donates electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process. Typical reducing agents undergo permanent chemical alteration through covalent or ionic reaction chemistry. This results in the complete and irreversible transfer of one or more electrons. In many chemical circumstances, however, the transfer of electronic charge to an electron acceptor may be only fractional, meaning an electron is not completely transferred, but results in an electron resonance between the donor and acceptor. This leads to the formation of charge transfer complexes in which the components largely retain their chemical identities. The electron donating power of a donor molecule is measured by its ionization potential which is the energy required to remove an electron from the highest occupied molecular orbital (HOMO). The overall energy balance (ΔE), i.e., energ ...
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Electron Acceptor
An electron acceptor is a chemical entity that accepts electrons transferred to it from another compound. It is an oxidizing agent that, by virtue of its accepting electrons, is itself reduced in the process. Electron acceptors are sometimes mistakenly called electron receptors. Typical oxidizing agents undergo permanent chemical alteration through covalent or ionic reaction chemistry, resulting in the complete and irreversible transfer of one or more electrons. In many chemical circumstances, however, the transfer of electronic charge from an electron donor may be only fractional, meaning an electron is not completely transferred, but results in an electron resonance between the donor and acceptor. This leads to the formation of charge transfer complexes in which the components largely retain their chemical identities. The electron accepting power of an acceptor molecule is measured by its electron affinity which is the energy released when filling the lowest unoccupied molecul ...
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Tetracyanoethylene
Tetracyanoethylene (TCNE) is organic compound with the formula . It is a colorless solid, although samples are often off-white. It is an important member of the cyanocarbons. Synthesis and reactions TCNE is prepared by brominating malononitrile in the presence of potassium bromide to give the KBr-complex, and dehalogenating with copper. Oxidation of TCNE with hydrogen peroxide gives the corresponding epoxide, which has unusual properties. In the presence of base, TCNE reacts with malononitrile to give salts of pentacyanopropenide: :C2(CN)2 + CH2(CN)2 -> NC)2C-C(CN)-C(CN)2 + CN- + 2H+ Redox chemistry TCNE is an electron acceptor. Cyano groups have low energy π* orbitals, and the presence of four such groups, with their π systems (conjugated) to the central double bond, gives rise to an electrophilic alkene. TCNE is reduced at -0.27 V vs ferrocene/ferrocenium: :C2(CN)4 + e- -> 2(CN)4 Because of its ability to accept an electron, TCNE has been used to prepare numerou ...
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Conjugated System
In theoretical chemistry, a conjugated system is a system of connected p-orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented as having alternating single and multiple bonds. Lone pairs, radicals or carbenium ions may be part of the system, which may be cyclic, acyclic, linear or mixed. The term "conjugated" was coined in 1899 by the German chemist Johannes Thiele. Conjugation is the overlap of one p-orbital with another across an adjacent σ bond (in transition metals, d-orbitals can be involved). A conjugated system has a region of overlapping p-orbitals, bridging the interjacent locations that simple diagrams illustrate as not having a π bond. They allow a delocalization of π electrons across all the adjacent aligned p-orbitals. The π electrons do not belong to a single bond or atom, but rather to a group of atoms. Molecules containing conjugated syst ...
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Heterocycle
A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two different chemical element, elements as members of its ring(s). Heterocyclic chemistry is the branch of organic chemistry dealing with the synthesis, properties, and applications of these heterocycles. Examples of heterocyclic compounds include all of the nucleic acids, the majority of drugs, most biomass (cellulose and related materials), and many natural and synthetic dyes. More than half of known compounds are heterocycles. 59% of US FDA-approved drugs contain nitrogen heterocycles. Classification The study of heterocyclic chemistry focuses especially on unsaturated derivatives, and the preponderance of work and applications involves unstrained 5- and 6-membered rings. Included are pyridine, thiophene, pyrrole, and furan. Another large class of heterocycles refers to those fused to benzene rings. For example, the fused benzene derivatives of pyridine, thiophene, pyrrole, and ...
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Ionization Potential
Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule is called an ion. Ionization can result from the loss of an electron after collisions with subatomic particles, collisions with other atoms, molecules and ions, or through the interaction with electromagnetic radiation. Heterolytic bond cleavage and heterolytic substitution reactions can result in the formation of ion pairs. Ionization can occur through radioactive decay by the internal conversion process, in which an excited nucleus transfers its energy to one of the inner-shell electrons causing it to be ejected. Uses Everyday examples of gas ionization are such as within a fluorescent lamp or other electrical discharge lamps. It is also used in radiation detectors such as the Geiger-Müller counter or the ionization chamber. The ionizat ...
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