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Pentacene () is a
polycyclic aromatic hydrocarbon A Polycyclic aromatic hydrocarbon (PAH) is any member of a class of organic compounds that is composed of multiple fused aromatic rings. Most are produced by the incomplete combustion of organic matter— by engine exhaust fumes, tobacco, incine ...
consisting of five linearly-fused
benzene Benzene is an Organic compound, organic chemical compound with the Chemical formula#Molecular formula, molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal Ring (chemistry), ring with one hyd ...
() rings. This highly conjugated compound is an
organic semiconductor Organic semiconductors are solids whose building blocks are pi-bonded molecules or polymers made up by carbon and hydrogen atoms and – at times – heteroatoms such as nitrogen, sulfur and oxygen. They exist in the form of molecular crystals o ...
. The compound generates
exciton An exciton is a bound state of an electron and an electron hole which are attracted to each other by the electrostatic Coulomb's law, Coulomb force resulting from their opposite charges. It is an electrically neutral quasiparticle regarded as ...
s upon absorption of ultra-violet ( UV) or visible
light Light, visible light, or visible radiation is electromagnetic radiation that can be visual perception, perceived by the human eye. Visible light spans the visible spectrum and is usually defined as having wavelengths in the range of 400– ...
; this makes it very sensitive to
oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
. For this reason, this compound, which is a purple powder, slowly degrades upon exposure to air and light. Structurally, pentacene is one of the linear
acene In organic chemistry, the acenes or polyacenes are a class of organic compounds and polycyclic aromatic hydrocarbons made up of benzene () rings which have been linearly fused. They follow the general molecular formula . The larger represent ...
s, the previous one being
tetracene Tetracene, also called naphthacene, is a polycyclic aromatic hydrocarbon. It has the appearance of a pale orange powder. Tetracene is the four-ringed member of the series of acenes. Tetracene is a molecular organic semiconductor, used in organi ...
(four fused benzene rings) and the next one being
hexacene Hexacene is an aromatic compound consisting of six linearly-fused benzene rings. It is a blue-green, air-stable solid with low solubility. Hexacene is one of a series of linear polycyclic molecules created by such aromatic ring fusions, a series ...
(six fused benzene rings). In August 2009, a group of researchers from
IBM International Business Machines Corporation (using the trademark IBM), nicknamed Big Blue, is an American Multinational corporation, multinational technology company headquartered in Armonk, New York, and present in over 175 countries. It is ...
published experimental results of imaging a single
molecule A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
of pentacene using an
atomic force microscope Atomic force microscopy (AFM) or scanning force microscopy (SFM) is a very-high-resolution type of scanning probe microscopy (SPM), with demonstrated resolution on the order of fractions of a nanometer, more than 1000 times better than the diffr ...
. In July 2011, they used a modification of
scanning tunneling microscopy A scanning tunneling microscope (STM) is a type of scanning probe microscope used for imaging surfaces at the atomic level. Its development in 1981 earned its inventors, Gerd Binnig and Heinrich Rohrer, then at IBM Zürich, the Nobel Prize in ...
to experimentally determine the shapes of the highest occupied and lowest unoccupied molecular orbitals. In 2012, pentacene-doped ''p''-terphenyl was shown to be effective as the amplifier medium for a room-temperature
maser A maser is a device that produces coherent electromagnetic waves ( microwaves), through amplification by stimulated emission. The term is an acronym for microwave amplification by stimulated emission of radiation. Nikolay Basov, Alexander Pr ...
.


Synthesis

The compound, originally called dinaphthanthracene after
naphthalene Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white Crystal, crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08 Parts-per notation ...
and
anthracene Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the production of the red dye alizarin and other dyes, as a scintil ...
(modern nomenclature for polyacenes, including pentacene, was only introduced in 1939 by
Erich Clar Erich Clar (23 August 1902 – 27 March 1987) was a German organic chemistry, organic chemist, born in Hřensko (a village directly at the border of Germany and the Czech Republic; Czech: Hřensko, German: Herrnskretschen), who studied polycyclic a ...
), was first synthesized in 1912 by British chemists
William Hobson Mills William Hobson Mills FRS (6 July 1873 – 22 February 1959) was a British organic chemist. Biography William Hobson Mills was born in Hammersmith on 6 July 1873, the eldest of five children of William Henry Mills, an architect, and Emily Wil ...
and Mildred May Gostling. A classic method for pentacene synthesis is by the
Elbs reaction The Elbs reaction is an organic reaction describing the pyrolysis of an ortho methyl substituted benzophenone to a condensed polyaromatic. The reaction is named after its inventor, the German chemist Karl Elbs, also responsible for the Elbs oxid ...
. Pentacenes can also be prepared by
extrusion Extrusion is a process used to create objects of a fixed cross section (geometry), cross-sectional profile by pushing material through a Die (manufacturing), die of the desired cross-section. Its two main advantages over other manufacturing pro ...
of a small volatile component (
carbon monoxide Carbon monoxide (chemical formula CO) is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the si ...
) from a suitable precursor at 150 °C. The precursor itself is prepared in three steps from two molecules of α,α,α',α'-tetrabromo-''o''-xylene with a 7-''tert''-butoxybicyclo .2.1epta-2,5-diene by first heating with
sodium iodide Sodium iodide (chemical formula NaI) is an ionic compound formed from the chemical reaction of sodium metal and iodine. Under standard conditions, it is a white, water-soluble solid comprising a 1:1 mix of sodium cations (Na+) and iodide anions ...
in
dimethylformamide Dimethylformamide, DMF is an organic compound with the chemical formula . Its structure is . Commonly abbreviated as DMF (although this initialism is sometimes used for 2,5-dimethylfuran, dimethylfuran, or dimethyl fumarate), this colourless liqui ...
to undergo a series of elimination and Diels–Alder reactions to form the ring system, then hydrolysing the ''tert''-butoxy group to an
alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...
and followed by its oxidation to the
ketone In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...
. The product is reported to have some solubility in
chloroform Chloroform, or trichloromethane (often abbreviated as TCM), is an organochloride with the formula and a common solvent. It is a volatile, colorless, sweet-smelling, dense liquid produced on a large scale as a precursor to refrigerants and po ...
and is therefore amenable to
spin coating Spin coating is a procedure used to deposit uniform thin films onto flat substrates. Usually a small amount of coating material in liquid form is applied on the center of the substrate, which is either spinning at low speed or not spinning at al ...
. Pentacene is soluble in hot chlorinated benzenes, such as
1,2,4-trichlorobenzene 1,2,4-Trichlorobenzene is an organochlorine compound, one of three isomers of trichlorobenzene. It is a derivative of benzene with three chloride substituents. It is a colorless liquid used as a solvent for a variety of compounds and materials. P ...
, from which it can be recrystallized to form platelets.


Pentacene derivatives


Monomeric pentacene derivatives

6,13-Substituted pentacenes are accessible through pentacenequinone by reaction with an aryl or alkynyl nucleophile (for example Grignard or organolithium reagents) followed by reductive aromatization. Another method is based on homologization of diynes by transition metals (through zirconacyclopentadienes) Functionalization of pentacene has allowed for control of the solid-state packing of this chromophore. The choice of the substituents (both size and location of substitution on the pentacene) influences the solid-state packing and can be used to control whether the compound adopts 1-dimensional or 2-dimensional cofacial
pi-stacking In chemistry, π-effects or π-interactions are a type of non-covalent interaction that involves π systems. Just like in an electrostatic interaction where a region of negative charge interacts with a positive charge, the electron-rich π system ...
in the solid-state, as opposed to the herringbone packing observed for pentacene. Although pentacene's structure resembles that of other aromatic compounds like
anthracene Anthracene is a solid polycyclic aromatic hydrocarbon (PAH) of formula C14H10, consisting of three fused benzene rings. It is a component of coal tar. Anthracene is used in the production of the red dye alizarin and other dyes, as a scintil ...
, its
aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...
properties are poorly defined; as such, pentacene and its derivatives are the subject of much research. A
tautomer In chemistry, tautomers () are structural isomers (constitutional isomers) of chemical compounds that readily interconvert. The chemical reaction interconverting the two is called tautomerization. This conversion commonly results from the reloca ...
ic
chemical equilibrium In a chemical reaction, chemical equilibrium is the state in which both the Reagent, reactants and Product (chemistry), products are present in concentrations which have no further tendency to change with time, so that there is no observable chan ...
exists between ''6-methylene-6,13-dihydropentacene'' and 6-methylpentacene. : This equilibrium is entirely in favor of the methylene compound. Only by heating a solution of the compound to 200 °C does a small amount of the pentacene develop, as evidenced by the emergence of a red-violet color. According to one study the
reaction mechanism In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical reaction occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage ...
for this equilibrium is not based on an intramolecular 1,5-hydride shift, but on a
bimolecular In chemistry, molecularity is the number of molecules that come together to react in an elementary reaction, elementary (single-step) reactionAtkins, P.; de Paula, J. Physical Chemistry. Oxford University Press, 2014 and is equal to the sum of Sto ...
free radical A daughter category of ''Ageing'', this category deals only with the biological aspects of ageing. Ageing Biogerontology Biological processes Causes of death Cellular processes Gerontology Life extension Metabolic disorders Metabolism ...
hydrogen migration. In contrast,
isotoluene The isotoluenes in organic chemistry are the non-aromatic toluene isomers with an exocyclic double bond. They are of some academic interest in relation to aromaticity and isomerisation mechanisms. The three basic isotoluenes are ''ortho''-isotol ...
s with the same central chemical motif easily aromatize. Pentacene reacts with elemental
sulfur Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...
in
1,2,4-trichlorobenzene 1,2,4-Trichlorobenzene is an organochlorine compound, one of three isomers of trichlorobenzene. It is a derivative of benzene with three chloride substituents. It is a colorless liquid used as a solvent for a variety of compounds and materials. P ...
to the compound hexathiapentacene.
X-ray crystallography X-ray crystallography is the experimental science of determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to Diffraction, diffract in specific directions. By measuring th ...
shows that all the carbon-to-sulfur
bond length In molecular geometry, bond length or bond distance is defined as the average distance between Atomic nucleus, nuclei of two chemical bond, bonded atoms in a molecule. It is a Transferability (chemistry), transferable property of a bond between at ...
s are roughly equal (170 pm); from this, it follows that
resonance structure In chemistry, resonance, also called mesomerism, is a way of describing bonding in certain molecules or polyatomic ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance structures'' or '' ...
s B and C with complete charge separation are more significant than structure A. : In the crystal phase the molecules display aromatic stacking interactions, whereby the distance between some sulfur atoms on neighboring molecules can become less (337 pm) than the sum of two
Van der Waals radii The van der Waals radius, ''r'', of an atom is the radius of an imaginary hard sphere representing the distance of closest approach for another atom. It is named after Johannes Diderik van der Waals, winner of the 1910 Nobel Prize in Physics, ...
(180 pm) Like the related
tetrathiafulvalene Tetrathiafulvalene (TTF) is an organosulfur compound with the formula . It is the parent of many tetrathiafulvenes. Studies on these heterocyclic compound contributed to the development of molecular electronics, although no practical applications ...
, this compound is studied in the field of
organic semiconductor Organic semiconductors are solids whose building blocks are pi-bonded molecules or polymers made up by carbon and hydrogen atoms and – at times – heteroatoms such as nitrogen, sulfur and oxygen. They exist in the form of molecular crystals o ...
s. The acenes may appear as planar and rigid molecules, but in fact they can be very distorted. The pentacene depicted below: : has an end-to end twist of 144° and is sterically stabilized by the six
phenyl In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula , and is often represented by the symbol Ph (archaically φ) or Ø. The phenyl group is closely related to benzene and can be viewed as a benzene ...
groups. The compound can be resolved into its two
enantiomer In chemistry, an enantiomer (Help:IPA/English, /ɪˈnænti.əmər, ɛ-, -oʊ-/ Help:Pronunciation respelling key, ''ih-NAN-tee-ə-mər''), also known as an optical isomer, antipode, or optical antipode, is one of a pair of molecular entities whi ...
s with an unusually high reported
optical rotation Optical rotation, also known as polarization rotation or circular birefringence, is the rotation of the orientation of the plane of polarization about the optical axis of linearly polarized light as it travels through certain materials. Circul ...
of 7400° although
racemization In chemistry, racemization is a conversion, by heat or by chemical reaction, of an optically active compound into a racemic (optically inactive) form. This creates a 1:1 molar ratio of enantiomers and is referred to as a racemic mixture (i.e. cont ...
takes place with a chemical half-life of 9 hours.


Oligomers and polymers of pentacene

Oligomers In chemistry and biochemistry, an oligomer () is a molecule that consists of a few repeating units which could be derived, actually or conceptually, from smaller molecules, monomers.Quote: ''Oligomer molecule: A molecule of intermediate relativ ...
and
polymers A polymer () is a substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeating subunits derived from one or more species of monomers. Due to their broad spectrum of properties, b ...
based on pentacene have been explored both synthetically as well as in device application settings. Polymer light emitting diodes (
PLED An organic light-emitting diode (OLED), also known as organic electroluminescent (organic EL) diode, is a type of light-emitting diode (LED) in which the emission (electromagnetic radiation), emissive electroluminescence, electroluminescent lay ...
s) have been constructed using conjugated copolymers (1a–b) containing fluorene and pentacene. A few other conjugated pentacene polymers (2a–b and 3) have been realized based on Sonogashira and
Suzuki is a Japanese multinational mobility manufacturer headquartered in Hamamatsu, Shizuoka Prefecture, Shizuoka. It manufactures automobiles, motorcycles, all-terrain vehicles (ATVs), outboard motor, outboard marine engines, wheelchairs and a va ...
coupling reactions of a dibromopentacene monomer. Non-conjugated pentacene-based polymers have been synthesized via esterification of a pentacene diol monomer with bis-acid chlorides to form polymers 4a–b.
Various synthetic strategies have been employed to form conjugated oligomers of pentacene 5a–c including a one-pot-four-bond forming procedure which provided a solution-processable conjugated pentacene dimer (5c) which exhibited photoconductive gain >10, placing its performance within the same order of magnitude as thermally evaporated films of non-functionalized pentacene which exhibited photoconductive gain >16 using analogous measurement techniques. A modular synthetic method to conjugated pentacene di-, tri- and tetramers (6–8) has been reported which is based on homo- and cross-coupling reactions of robust dehydropentacene intermediates. Non-conjugated oligomers 9–10 based on pentacene have been synthesized, including dendrimers 9–10 with up to 9 pentacene moieties per molecule with molar absorptivity for the most intense absorption > 2,000,000 M−1•cm−1. Dendrimers 11–12 were shown to have improved performance in devices compared to analogous pentacene-based polymers 4a–b in the context of photodetectors.


Materials research

Pentacenes have been examined as potential dichroic dyes. The pentacenoquinone displayed below is
fluorescent Fluorescence is one of two kinds of photoluminescence, the emission of light by a substance that has absorbed light or other electromagnetic radiation. When exposed to ultraviolet radiation, many substances will glow (fluoresce) with color ...
and when mixed with liquid crystal E7 mixture a dichroic ratio of 8 is reached. Longer acenes align better in the
nematic Liquid crystal (LC) is a state of matter whose properties are between those of conventional liquids and those of solid crystals. For example, a liquid crystal can flow like a liquid, but its molecules may be oriented in a common direction as i ...
liquid crystal Liquid crystal (LC) is a state of matter whose properties are between those of conventional liquids and those of solid crystals. For example, a liquid crystal can flow like a liquid, but its molecules may be oriented in a common direction as i ...
phase. : Combined with
buckminsterfullerene Buckminsterfullerene is a type of fullerene with the formula . It has a cage-like fused-ring structure ( truncated icosahedron) made of twenty hexagons and twelve pentagons, and resembles a football. Each of its 60 carbon atoms is bonded to i ...
, pentacene is used in the development of organic photovoltaic prototypes. Organic photovoltaic cells are cheaper and more flexible than traditional inorganic cells, which could potentially open doors to solar cells in new markets. Pentacene is a popular choice for research on organic
thin-film transistor A thin-film transistor (TFT) is a special type of field-effect transistor (FET) where the transistor is made by thin film deposition. TFTs are grown on a supporting (but non-conducting) substrate, such as glass. This differs from the convention ...
s and
OFET An organic field-effect transistor (OFET) is a field-effect transistor using an organic semiconductor in its channel. OFETs can be prepared either by vacuum evaporation of small molecules, by solution-casting of polymers or small molecules, or ...
s, being one of the most thoroughly investigated conjugated organic molecules with a high application potential due to a hole mobility in OFETs of up to 5.5 cm2/(V·s), which exceeds that of amorphous silicon. Pentacene, as well as other organic conductors, is subject to rapid oxidation in air, which precludes commercialization. If the pentacene is preoxidized, the pentacene-quinone is a potential gate insulator, then the mobility can approach that of
rubrene Rubrene (5,6,11,12-tetraphenyltetracene) is the organic compound with the formula . It is a red colored polycyclic aromatic hydrocarbon. Because of its distinctive optical and electrical properties, rubrene has been extensively studied. It has be ...
– the highest-mobility organic semiconductor – namely, 40 cm2/(V·s). This pentacene oxidation technique is akin to the silicon oxidation used in the silicon electronics.


See also

* Perfluoropentacene


References


External links


facts about pentacene
retrieved Apr. 17, 2006

New Scientist, ''2 December 2007''

IBM images Pentacene, the first molecule imaged in detail ''29 August 2009'' {{PAHs Organic semiconductors Acenes Polycyclic aromatic hydrocarbons Pentacyclic compounds