EP2773687A1 - Thiophènes fusionnés, procédés de fabrication de thiophènes fusionnés et leurs utilisations - Google Patents

Thiophènes fusionnés, procédés de fabrication de thiophènes fusionnés et leurs utilisations

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Publication number
EP2773687A1
EP2773687A1 EP12845124.2A EP12845124A EP2773687A1 EP 2773687 A1 EP2773687 A1 EP 2773687A1 EP 12845124 A EP12845124 A EP 12845124A EP 2773687 A1 EP2773687 A1 EP 2773687A1
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EP
European Patent Office
Prior art keywords
substituted
compound
thiophene
unsubstituted
fused thiophene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12845124.2A
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German (de)
English (en)
Other versions
EP2773687A4 (fr
Inventor
Mingqian He
Jianfeng Li
James Robert Matthews
Weijun Niu
Arthur L. WALLACE
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Corning Inc
Original Assignee
Corning Inc
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Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Publication of EP2773687A1 publication Critical patent/EP2773687A1/fr
Publication of EP2773687A4 publication Critical patent/EP2773687A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers

Definitions

  • compositions including heterocyclic organic compounds More specifically, described herein are fused thiophene compounds, methods for making them, and uses thereof.
  • Highly conjugated organic materials are currently the focus of great research activity, chiefly due to their interesting electronic and optoelectronic properties. They are being investigated for use in a variety of applications, including field effect transistors (FETs), thin-film transistors (TFTs), organic light-emitting diodes (OLEDs), electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, and as non-linear optical (NLO) materials.
  • FETs field effect transistors
  • TFTs thin-film transistors
  • OLEDs organic light-emitting diodes
  • EO electro-optic
  • Highly conjugated organic materials may find utility in devices such as RFID tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices.
  • Oligomers and polymers of fused thiophenes such as oligo- or poly(thieno[3,2-Z?]thiophene (2) and oligo- or poly(dithieno[3,2-Z?:2'-3 '- ⁇ i]thiophene) (1)
  • fused thiophene-based materials have also been suggested for use in electronic and optoelectronic devices, and have been shown to have acceptable conductivities and non-linear optical properties.
  • unsubstituted fused thiophene-based materials tend to suffer from low solubility, marginal processability and oxidative instability.
  • fused thiophene-based materials having acceptable solubility, processability and oxidative stability.
  • compositions including heterocyclic organic compounds such as fused thiophene compounds are compositions including heterocyclic organic compounds such as fused thiophene compounds, methods for making them, and uses thereof.
  • the compositions and methods described herein possess a number of advantages over prior art compositions and methods.
  • the fused thiophene compositions described herein can be made to be more soluble and processable than the analogous unsubstituted thiophene compositions.
  • Polymers and oligomers including the fused thiophene moieties described herein can be made to be processable using conventional spin-coating operations.
  • the compositions described herein can be made with substantially no ⁇ - ⁇ content, greatly improving the oxidative stability of the compositions.
  • Ri and R2 are, independently, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether; R 3 and R4 are, independently, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, hal
  • a and B are O. In some embodiments, A and B are S. In some embodiments, at least one of Ri and R2 comprises a substituted or unsubstituted alkyl. In some embodiments, at least one of Ri and R2 comprises an unsubstituted alkyl. In some embodiments, at least one of R3 and R4 comprises a substituted or unsubstituted alkyl. In some embodiments, at least one of R3 and R4 comprises a substituted or unsubstituted alkyl group comprising at least six carbon atoms. In some embodiments, n is from 1 to 15.
  • the compound is incorporated into a conjugated fused thiophene polymer or oligomer having m > 1.
  • the compound comprises a polymer.
  • the polymer has a molecular weight from about 4000 to about 180,000 Da.
  • the polymer has a molecular weight from about 15,000 to about 50,000 Da.
  • the polymer has a molecular weight from about 20,000 to about 40,000 Da.
  • FIG. 1 is a reaction scheme showing a method for making a ⁇ ''-R-substituted fused thiophene moieties.
  • FIG. 2 is a reaction scheme showing a method for making an a-(R-acyl)-P- carboxymethylthio thiophene moiety.
  • FIG. 3 is a reaction scheme showing a method for making an a'-hydro-P"-R- substituted fused thiophene moiety.
  • FIG. 4 is a reaction scheme in which there is a simultaneous cyclization on both sides of a thiophene moiety.
  • FIG. 5 is a reaction scheme showing an alternative method for making an ⁇ , ⁇ '- bis(R-acyl)-P,P'-bis(carboxymethylthio) thiophene moiety.
  • FIG. 6 is a reaction scheme showing a method for making a five-ring fused thiophene.
  • FIG. 7 is a reaction scheme showing a method for making polycyclic ⁇ -R- substituted-P'-bromo thiophene moieties.
  • FIG. 8 is a reaction scheme showing a method for making P-R-substituted-P'- bromo thiophene compounds.
  • FIG. 9 is reaction scheme showing a method for making monosubstituted fused thiophene moieties.
  • FIG. 10 is a reaction scheme showing the synthesis of 3,6-dihexylthieno[3,2- Z?]thiophene and 3,6-didecylthieno[3,2-Z?]thiophene according to Example 1.
  • FIG. 11 is a reaction scheme showing the synthesis of 3-hexylthieno[3,2- Z?]thiophene according to Example 2.
  • FIG. 12 is a reaction scheme showing the synthesis of 3,6-didecylthieno[3,2- Z?]thiophene and 3,6-didecylthieno[3,2-Z?]thiophene-4,4-dioxide according to Example 3.
  • FIG. 13 is a reaction scheme showing the synthesis of 3,7-didecylthieno[3,2- Z?]thieno[2',3':4,5]thieno[2,3-i/]thiophene according to Example 4.
  • FIG. 14 is a reaction scheme showing the failed synthesis of ⁇ -hexyl- substituted thieno[2,3-i/]thiophene according to conventional methodologies as described in Example 5.
  • FIG. 15A and FIG. 15B are reaction schemes for the synthesis 2-2 and 3-3 dimers and 5- and 7 -ring systems according to Example 7.
  • FIG. 16 is a reaction scheme for the synthesis of a seven-ring tetraalkylsubstituted thienothiophene according to Example 8.
  • FIG. 17 is a reaction scheme for the synthesis of a nine-ring tetraalkylsubstituted thienothiophene according to Example 8.
  • FIG. 18 is a reaction scheme for producing fused thiophene copolymers.
  • FIG. 19A and FIG. 19B show structures of different fused thiophene copolymers produced by the methods described herein.
  • FIG. 20 shows a reaction scheme for forming the bis-tin-substituted FT4 from dibromo-FT4 by sequential reaction with butyllithium and trimethyltinchloride.
  • FIG. 23 shows that the polymeric poly[(3,7-diheptadecylthieno[3,2- b]thieno[2',3 ' :4,5]thieno[2,3-d]thiophene-2,6-diyl)[2,5-dihexadecyl-3,6-di(thiophen-2- yl)pyrrolo [3 ,4-c]pyrrole- 1 ,4(2H,5H)-dione] -5,5 ' -diyl ("PTDC 16DPPTDC 17FT4") material was thermally stable to temperatures over 400°C. This is indicative of the stability of the polymer.
  • FIG. 24 shows UV-visible spectra of a chloroform solution and solid film of the PTDC16DPPTDC17FT4 polymer. Both species show a broad absorption from about 550 nm to about 950 nm and a less intense absorption from around 300 to 500 nm. These absorptions give the polymer a dark, almost green-black appearance which may be useful for photovoltaic systems.
  • FIG. 25 describes the reaction scheme for forming a conjugated polymer comprising a FT4 coupled by a 4,7-benzo[c]-l,2,5-thiazole.
  • Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. [0042] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.
  • alkyl group is a branched or unbranched saturated hydrocarbon group of 1 to 40 carbon atoms, such as methyl, ethyl, n -propyl, isopropyl, M-butyl, isobutyl, i-butyl, pentyl, hexyl, heptyl, octyl, decyl, or tetradecyl, and the like.
  • the alkyl group can be substituted or unsubstituted.
  • unsubstituted alkyl group is defined herein as an alkyl group composed of just carbon and hydrogen.
  • substituted alkyl group is defined herein as an alkyl group with one or more hydrogen atoms substituted with a group including, but not limited to, an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, or a halide, an acyl halide, an acrylate, or a vinyl ether.
  • the alkyl groups can be an alkyl hydroxy group, where any of the hydrogen atoms of the alkyl group are substituted with a hydroxyl group.
  • alkyl group as defined herein also includes cycloalkyl groups.
  • cycloalkyl group as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms, and in some embodiments from three to 20 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • the term cycloalkyl group also includes a heterocycloalkyl group, where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.
  • aryl group as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc.
  • aryl group also includes “heteroaryl group,” meaning an aromatic ring composed of at least three carbon atoms that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy as defined herein.
  • the term "aryl group” is limited to substituted or unsubstituted aryl and heteroaryl rings having from three to 30 carbon atoms.
  • aralkyl as used herein is an aryl group having an alkyl group as defined above attached to the aryl group.
  • An example of an aralkyl group is a benzyl group.
  • alkenyl group is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms and structural formula containing at least one carbon- carbon double bond.
  • alkynyl group is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms and a structural formula containing at least one carbon- carbon triple bond.
  • conjugated group is defined as a linear, branched or cyclic group, or combination thereof, in which p-orbitals of the atoms within the group are connected via delocalization of electrons and wherein the structure can be described as containing alternating single and double or triple bonds and may further contain lone pairs, radicals, or carbenium ions.
  • Conjugated cyclic groups may comprise both aromatic and non-aromatic groups, and may comprise polycyclic or heterocyclic groups, such as diketopyrrolopyrrole. Ideally, conjugated groups are bound in such a way as to continue the conjugation between the thiophene moieties they connect. In some embodiments, "conjugated groups” is limited to conjugated groups having three to 30 carbon atoms.
  • each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • any subset or combination of these is also specifically contemplated and disclosed.
  • the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions.
  • steps in methods of making and using the disclosed compositions are if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
  • compositions comprising at least one fused thiophene moiety com rising the formula 3 or 4
  • composition comprising at least one moiety comprising the formula 3 ' or 4'
  • n is an integer greater than zero; in some embodiments, n is an integer of 2 or more; m is an integer greater than zero; in some embodiments, m is an integer of two or more; o is an integer greater than zero; x is an integer greater than or equal to one; Ri and R2 are, independently, hydrogen or an alkyl group, wherein at least one of Ri and R 2 is an alkyl group, and Ar is an aryl group, wherein n is not one.
  • the fused thiophene ring system of a fused thiophene moiety is the heterocyclic core of the moiety, and does not include the a-substituents and the ⁇ -substituents (e.g. Ri and R2) bound to the fused thiophene ring system.
  • the fused thiophene moieties described herein can have any number of fused rings.
  • the methods described herein permit the construction of fused thiophene moieties having any desired number of rings.
  • n is 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, or 15.
  • n is 2 or more.
  • m is 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, or 15.
  • o is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, or 15.
  • the fused thiophene moiety can be tricyclic or greater (i.e., 4 or 4', n 1 ; or 3 or 3', n>2).
  • the fused thiophene moiety can be tetracyclic or greater (i.e., 4 or 4', n >2; or 3 or 3', n>2).
  • composition comprises at least one moiety comprising the formula 3" or 4"
  • Ri and R 2 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether;
  • R 3 and R4 are, independently, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether; and, A and B are, independently, either S or O.
  • the fused thiophene moieties described in 3" and 4" can have any number of fused rings above 3.
  • the methods described herein permit the construction of fused thiophene moieties having any desired number of rings.
  • n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, or 15.
  • fused thiophene moieties described herein are substituted at least one of the ⁇ -positions of the fused thiophene ring system with an alkyl group.
  • an a-position of a fused thiophene ring system is a non-fused carbon center that is directly adjacent to the sulfur of a fused thiophene, while a ⁇ -position is a non-fused carbon center that is separated from the sulfur of the fused thiophene by an a-position.
  • the a-positions are shown as being connected to the rest of the composition, while the ⁇ -positions are substituted with Ri and R2.
  • At least one of Ri and R 2 is an alkyl group.
  • methods conventionally used to alkylate simple unfused thiophenes fail when used in attempts to alkylate fused thiophene ring systems.
  • described herein are methods for making fused thiophene moieties having large alkyl substitution at the ⁇ -positions of the fused thiophene ring system.
  • Ri and R 2 can be a variety of substituted or unsubstituted alkyl groups.
  • at least one of Ri or R 2 is an unsubstituted alkyl group.
  • the unsubstituted alkyl group can be a straight-chain alkyl group (e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or hexadecyl), a branched alkyl group (e.g.
  • Ri or R2 is an alkyl group, itself at least four carbons in size, which is substituted.
  • substitution of the alkyl group is separated from the fused thiophene ring system by at least two carbons.
  • Ri and/or R 2 can be substituted with an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, or a halide, acyl halide, an acrylate, or a vinyl ether.
  • substituted alkyl groups include, but are not limited to, 6- hydroxyhexyl and 3-phenylbutyl.
  • the selection of Ri and R2 will depend on the end use of the fused thiophene moiety-containing composition. The methods described herein permit the synthesis of fused thiophene moieties having a wide variety of Ri and R2 substituents. Any functionality on a substituted alkyl group can be protected in order to survive subsequent reaction steps.
  • Ri and R2 can be an alkyl group having at least six carbons in size.
  • the alkyl group can have the formula Ckttk + i, where k is an integer greater than or equal to six.
  • the fused thiophene ring system is substituted at both ⁇ - positions, so that there are no ⁇ -hydrogens on the ring system.
  • neither Ri nor R 2 in structures 3, 3', 3", 4, 4', and 4" is H.
  • Such moieties can be incorporated in oligomers and polymers having substantially no ⁇ -hydrogen content, and will have increased oxidative stability.
  • the molar ratio of ⁇ -hydrogen to fused thiophene ring system can be less than about 1/6, 1/7, 1/8, 1/9, or 1/10.
  • one or both of Ri and R2 can be an alkyl group.
  • Ri and R2 are identical alkyl groups.
  • Ri and R2 are identical, regioregular polymers can be easily constructed because the problems of regioselectivity (i.e. head-to-tail vs. head-to- head coupling) of polymerization reactions disappear.
  • Ri and R2 may also be different.
  • Ri can be at least four carbons in size, with R2 being less than four carbons in size (e.g., a methyl group).
  • both R 1 and R 2 can be at least four carbons in size.
  • an aryl group (Ar) is attached to the a-position of the fused thiophene moiety.
  • Ar comprises one or more unfused thiophene groups, one or more fused thiophene groups, or a combination of unfused and fused thiophene groups.
  • the moiety comprises the formula 200 or 201
  • o is lor more; in some embodiments, o is 1, 2, or 3 ; and R3 and R4 are, independently, hydrogen or an alkyl group.
  • n is 2, 3, or 4, and m is 1.
  • n is 2, 3, or 4; m is one; and 0 is 1, 2, or 3.
  • the fused thiophene can be one fused thiophene group or two or more fused thiophene groups.
  • the fused thiophene groups can be the same or different.
  • Ar can be a bis-fused thiophene covalently bonded to a tris-fused thiophene.
  • Ar can be one or more substituted or unsubstituted thiophene groups bonded to a substituted or unsubstituted fused thiophene group.
  • the Ar moiety comprises 300 or 301
  • R3 and R4 are R3 and R4 are, independently, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether, and X and Y are independently covalent bonds or one or more aryl groups, one of which ultimately links to the fused thiophene moiety.
  • any of the sulfur atoms present in the fused thiophene compounds described herein can be oxidized to produce a SO2 group.
  • a composition includes at least one of the following oxidized fused thiophene moieties:
  • n is an integer greater than zero; in some embodiments, n is an integer of 2 or greater; m is no less than one; Ri and R2 are, independently, hydrogen or an alkyl group, wherein each T is, independently, S or SO2, wherein T is SO2 in at least one of the central-most rings of the oxidized fused thiophene ring system. Each T is independently S and SO2, where T is SO2 in at least one of the central-most rings of the fused thiophene ring system.
  • the central-most ring of a fused thiophene ring system having an odd number 2q+l of fused rings is the q+l th ring from an end of the ring system.
  • the central-most rings of a fused thiophene ring system having an even number 2q of fused rings are the q and q+1 rings from an end of the ring system.
  • the central -most ring of a three-ring system is the second ring
  • the central-most rings of a four-ring system are the second and third rings
  • the central-most ring of a five-ring system is the third ring.
  • the oxidized moiety comprises the formula 44' or 45'
  • T is SO2 in at least one of the central-most rings of the oxidized fused thiophene ring system.
  • T in at least one of the central-most rings is SO2 and the remaining S atoms are not oxidized.
  • any of the oxidized fused thiophene compounds described herein can be used in polymers, oligomers, monomers, chromophores, and other compositions as described above.
  • the at least one oxidized fused thiophene moiety can be present in the composition at a total concentration of at least 1 wt%.
  • the value of n can be, for example, 1, 2, 3, 4, or 5.
  • the fused thiophene moiety is tricyclic or greater (i.e., 45', n>l ; or 44', n>l). In some embodiments, n is 2 or more.
  • At least one of Ri and R2 is an alkyl group at least six carbons in size directly bound to the oxidized fused thiophene ring system core of the oxidized fused thiophene moiety.
  • Both Ri and R2 can be alkyl groups, and can be the same as or different from one another.
  • neither Ri nor R2 is H.
  • the composition has a ratio of ⁇ -hydrogen to oxidized fused thiophene ring systems of less than about 1/10, 1/9, 1/8, 1/7, or 1/6.
  • the oxidized fused compounds have the structure
  • Ri and R2 are, independently, hydrogen or an alkyl group
  • Q is, independently, hydrogen, a substituted or unsubstituted alkyl group, an acyl halide, an ester, an aldehyde, a ketone, a hydro xyl group, a thiol group or alkyl substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl ether, a hydroxy alkyl group, a carboxylic acid group, or a halide.
  • fused thiophene moieties of structures 3, 3', 3", 4, 4', 4", 44' and 45' can exist as simple monomeric fused thiophenes, or can be incorporated into more complex compounds, such as oligomers or polymers.
  • the fused thiophene moieties described in 3 and 4 can be incorporated in simple fused thiophene monomers having the formulae 7 and 8
  • n is an integer greater than zero; in some embodiments, n is an integer of 2 or more; R ⁇ and I3 ⁇ 4 are, independently, hydrogen or alkyl; and Q is, independently, hydrogen, a substituted or unsubstituted alkyl group (e.g., an alkyl hydroxy group), a carboxylic acid, an acyl halide, an ester, an aldehyde, a ketone, a hydroxyl group, a thiol group or alkyl substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl ether, or a halide.
  • each Q in 7 and 8 is bromide.
  • monomers having structures 7 and 8 can be used to make fused thiophene oligomers and polymers, as described below.
  • fused thiophene monomers 7 and 8, or alternatively oxidized fused thiophene monomers 44 and 45 can be incorporated in oligomers and polymers having conjugated homo-oligomeric or homopolymeric blocks of the fused thiophene moieties to produce polymers having the fused thiophene moieties 3, 3', 3", 4, 4', or 4", or 44' and 45'.
  • an oligomer or polymer includes a fused thiophene of structure 3, 3', 3", 4, 4', 4", 44' and 45' in which m is greater than 1. In further embodiments, m is at least about four.
  • m is at least about 10.
  • the monomers 7 or 8 (or, alternatively 44 or 45) can be polymerized to produce a homopolymer composed of residues having the formula 3 or 4 (or alternatively 44' or 45').
  • m is from 1 to 10,000, 1 to 9,000, 1 to 8,000, 1 to 7,000, 1 to 6,000, 1 to 5,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, 1 to 1,000, 1 to 500, 1 to 250, 1 to 100, 1 to 50, 1 to 25, 1 to 10, 25 to 1000, 25 to 500, 25 to 250, 50 to 1000, 50 to 500, or 50 to 250.
  • the fused thiophene monomers described herein can be incorporated into conjugated copolymers with other aromatic or unsaturated moieties.
  • the fused thiophene monomers 7 and 8 (or, alternatively 44 or 45) can be copolymerized with other substituted or unsubstituted fused thiophene moieties to form a conjugated fused thiophene polymer or oligomer.
  • the fused thiophene monomers 7 and 8 can be copolymerized with substituted or unsubstituted thiophenes to form thiophene/fused thiophene polymers or oligomers.
  • the fused thiophene monomers 7 and 8 (44 or 45) can also be copolymerized with other moieties commonly used in conjugated polymers, such as vinylene, phenylene, or other arylene or heteroarylene moieties.
  • fused thiophene moieties described herein can be incorporated into a wide variety of other types of polymers.
  • the fused thiophenes having the formula 7 and 8 (44 or 45) can be incorporated into the main chain of a polymer such as, for example, a polyester, a polyurethane, a polyether, a polyamide, a polycarbonate, or a polyketone; and in the side chain of a polymer such as, for example, a polyacrylate, a polymethacrylate, or a poly( vinyl ether).
  • fused thiophenes having the formula 7 and 8 can be modified with reactive groups (e.g., acyl chloride, alcohol, acrylate, amine, vinyl ether) that will permit the incorporation of the monomer into the polymer.
  • reactive groups e.g., acyl chloride, alcohol, acrylate, amine, vinyl ether
  • R 1 , R 2 , and/or Q can be modified with such reactive groups.
  • the moieties 3', 3", 4', 4", 44' and 45' can be incorporated in oligomers and polymers having conjugated homo-monomeric (i.e., single), homo- oligomeric, or homopolymeric blocks of the 3', 3", 4', 4", 44' and 45' moieties to produce polymers.
  • an oligomer or polymer includes a fused thiophene of structure 3', 3", 4', 4", 44' and 45' in which m is greater than 1.
  • m is at least about four.
  • m is at least about 10.
  • the moieties 3', 3", 4', 4", 44' and 45' can be polymerized to produce a homopolymer.
  • m is from 1 to 10,000, 1 to 9,000, 1 to 8,000, 1 to 7,000, 1 to 6,000, 1 to 5,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, 1 to 1,000, 1 to 500, 1 to 250, 1 to 100, 1 to 50, 1 to 25, 1 to 10, 25 to 1000, 25 to 500, 25 to 250, 50 to 1000, 50 to 500, or 50 to 250.
  • the polymers having conjugated homo-monomeric (i.e., single), homo-oligomeric, or homopolymeric blocks of the 3', 3", 4', 4", 44' and 45' moieties have molecular weights from about 4,000 to about 180,000 Da. In some embodiments, the polymers have molecular weights from about 15,000 to about 50,000 Da. In some embodiments, the polymers have molecular weights from about 20,000 to about 40,000 Da.
  • the molecular weight of the polymers having conjugated homo-monomeric (i.e., single), homo-oligomeric, or homopolymeric blocks of the 3', 3", 4', 4", 44' and 45' moieties have molecular weights from about 4,000 to about 180,000, about 4,000 to about 160,000, about 4,000 to about 140,000, about 4,000 to about 120,000, about 4,000 to about 100,000, about 4,000 to about 80,000, about 4,000 to about 70,000, about 4,000 to about 60,000, about 4,000 to about 50,000, about 4,000 to about 40,000, about 4,000 to about 30,000, about 5,000 to about 180,000, about 5,000 to about 160,000, about 5,000 to about 140,000, about 5,000 to about 120,000, about 5,000 to about 100,000, about 5,000 to about 80,000, about 5,000 to about 70,000, about 5,000 to about 60,000, about 5,000 to about 50,000, about 5,000 to about 40,000, about 5,000 to about 30,000, about 10,000 to about 180,000, about 10,000 to about 10,000 to about
  • the molecular weight of the polymers having conjugated homo- monomeric (i.e., single), homo-oligomeric, or homopolymeric blocks of the 3', 3", 4', 4", 44' and 45' moieties have molecular weights of about 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10,000, 15,000, 20,000, 25,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 1 10,000, 120,000, 130,000, 140,000 150,000, 160,000, 170,000, or 180,000 Da.
  • the moieties 3', 3", 4', 4", 44' and 45' can be incorporated into conjugated copolymers with other aromatic or unsaturated moieties.
  • the moieties 3', 3", 4', 4", 44' and 45' can be copolymerized with other substituted or unsubstituted fused thiophene moieties to form a conjugated fused thiophene polymer or oligomer.
  • the moieties 3', 3", 4', 4", 44' and 45' can be copolymerized with substituted or unsubstituted thiophenes to form thiophene/fused thiophene polymers or oligomers.
  • moieties 3', 3", 4', 4", 44' and 45' can also be copolymerized with other moieties commonly used in conjugated polymers, such as vinylene, phenylene, or other arylene or heteroarylene moieties.
  • moieties 3', 3", 4', 4", 44' and 45' described herein can be incorporated into a wide variety of other types of polymers.
  • the moieties 3', 3", 4', 4", 44' and 45' can be incorporated into the main chain of a polymer such as, for example, a polyester, a polyurethane, a polyether, a polyamide, a polycarbonate, or a polyketone; and in the side chain of a polymer such as, for example, a polyacrylate, a polymethacrylate, or a poly( vinyl ether).
  • moieties 3', 3", 4', 4", 44' and 45' can be modified with reactive groups (e.g., acyl chloride, alcohol, acrylate, amine, vinyl ether) that will permit the incorporation of the monomer into the polymer.
  • reactive groups e.g., acyl chloride, alcohol, acrylate, amine, vinyl ether
  • fused thiophenes described herein can also be incorporated in donor-acceptor chromophores, such as those commonly used in polymeric electro-optic materials.
  • donor-acceptor chromophores such as those commonly used in polymeric electro-optic materials.
  • the fused thiophene moieties of structures 3 and 4 can be incorporated into a donor-acceptor chromophore having the structure 9 or 10:
  • D is an electron donating group
  • A is an electron accepting group.
  • Donor- acceptor chromophores are described in more detail in U.S. Pat. Nos. 6,584,266; 6,514,434; 6,448,416; 6,444,830; and 6,393, 190, each of which is hereby incorporated herein by reference in its entirety.
  • the fused thiophene having the formula 7 or 8 can be reacted with an electron donating group and electron accepting group to produce compounds having the formula 9 and 10, respectively.
  • the compositions described herein have a sufficiently high concentration of the fused thiophene moieties of structures 3 or 4 (or 44 or 45) to yield a desired electronic or optoelectronic property to the composition.
  • the compositions have at least one fused thiophene moiety of structures 3 or 4 (or, alternatively 44 or 45) in a total concentration of at least 1 wt %.
  • the compositions described herein have at least one fused thiophene moiety of structures 3 or 4 (or 44 or 45) in a total concentration of at least 3 wt%.
  • the composition has at least one fused thiophene moiety of structures 3 or 4 (or 44 or 45) in higher total concentrations of, for example, at least 10 wt %, 20 wt %, 30 wt %, 40 wt %, or 50 wt %. Due to the presence of an alkyl group at the ⁇ -position of the fused thiophene ring, the compositions can have higher concentrations of fused thiophene moieties yet remain soluble and processable.
  • compositions described herein can be used to make a wide variety of devices.
  • the device can be a fused thiophene moiety-containing composition configured in an electronic, optoelectronic, or nonlinear optical device.
  • the compositions described herein can also be used in field effect transistors (FETs), thin-film transistors (TFTs), organic light-emitting diodes (OLEDs), PLED applications, electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, as non-linear optical (NLO) materials, as RFID tags, as electroluminescent devices in flat panel displays, in photovoltaic devices, and as chemical or biological sensors.
  • FETs field effect transistors
  • TFTs thin-film transistors
  • OLEDs organic light-emitting diodes
  • EO electro-optic
  • conductive materials as two photon mixing materials
  • organic semiconductors as non-linear optical (NLO) materials
  • RFID tags as electroluminescent devices in flat panel
  • the fused thiophene-based polymers embodied herein have unexpectedly high hole mobilities, on/off ratios, or low threshold voltages when incorporated into thin- film devices.
  • the hole mobilities of the fused thiophene-based polymers embodied herein are greater than 0.5 cm 2 /V-s, 0.75 cm 2 /V-s, 1.0 cm 2 /V-s, 1.25 cm 2 /V-s, 1.5 cm 2 /V-s, 1.75 cm 2 /V-s, 2.0 cm 2 /V-s, 2.25 cm 2 /V-s, 2.5 cm 2 /V-s, 2.75 cm 2 /V-s, 3.0 cm 2 /V-s, 3.25 cm 2 /V-s, 3.5 cm 2 /V-s, 3.75 cm 2 /V-s, or 4.0 cm 2 /V-s.
  • the fused thiophene-based polymers embodied herein have an on/off ratio of greater than 10 5 , 10 6 , 10 7 , 10 8 , 10 9 , or 10 10 . In some embodiments, the fused thiophene-based polymers embodied herein have a threshold voltage less than 0.25 V, 0.5 V, 0.75 V, 1.0 V, 1.25 V, 1.5 V, 1.75 V, 2.0 V, 2.25 V, 2.5 V, 2.75 V, 3.0 V, 3.25 V, 3.5 V, 3.75, or 4.0 V.
  • the polymers also display liquid crystalline phases over certain temperature ranges.
  • the liquid crystalline properties can easily be tuned by changing the length of the alkyl groups R ⁇ and I3 ⁇ 4.
  • the polymers also have good solubility in organic solvents such as, for example, toluene, chlorobenzene, which permits the casting of thin films using techniques known in the art.
  • the method for making a ⁇ ''-R-substituted fused thiophene moiety comprises the steps of:
  • a method for making a ⁇ ''-R-substituted fused thiophene compound is shown in the reaction scheme of FIG. 1.
  • an a-hydro-P-bromo thiophene moiety 11 is provided.
  • the a-hydro-P-bromo thiophene moiety 11 can be a simple unfused thiophene, as shown in structures 12 and 13 below.
  • Structure 12 is an unsubstituted unfused a-hydro-P-bromo thiophene, which upon ring fusion produce thienothiophene 14 having a single ⁇ substitution.
  • Structure 13 is R' substituted at the ⁇ ' center (i.e., a a-hydro-P-bromo-P'-R'-substituted thiophene), which upon ring fusion produces a doubly ⁇ -substituted thienothiopene 15.
  • R-acyl is meant to denote radical structure 17 below
  • carboxymethylthio is meant to denote radical structure 18 below
  • Z is the terminus of the carboxylate (which may be, e.g., H, substituted alkyl, unsubstituted alkyl). In some embodiments, Z is H, methyl, ethyl or propyl.
  • a-hydro-P-bromo thiophene moiety 11 is first acylated at the a-position with a R-acyl moiety using RCOC1 and AICI 3 , where R is an alkyl group having at least four carbons.
  • the acylated product is reacted with the 2-mercaptoacetate HSCH2COOZ to yield the a-(R-acyl)-P-carboxymethylthio thiophene moiety 16. While in the reaction scheme of FIG. 2, the R-acylation is performed first, in certain cases the reactions can be performed in the opposite order.
  • a-(R-acyl)-P-carboxymethylthio thiophene moiety 16 is then cyclized (e.g., via a base-catalyzed condensation, often under the same conditions as the reaction with the 2-mercaptoacetate) to yield an a"-carboxy-P"-R-substituted fused thiophene moiety 19, which is decarboxylated to form the ⁇ ''-R-substituted fused thiophene moiety 20, where R is an alkyl group having at least four carbons.
  • the acylation step may not be specific to the exposition. For example, as shown in the reaction scheme of FIG.
  • a,a'-dihydro-P- bromo thiophene moiety 21 is acylated and reacted with a 2-mercaptoacetate, forming a mixture of products including the desired a-(R-acyl)-a'-hydro-P-carboxymethylthio thiophene moiety 22, as well as the undesired regioisomeric a'-hydro-a-(R-acyl)-P- carboxymethylthio thiophene moiety 23.
  • regioisomer 22 will cyclize to form a'-hydro-a"-carboxy-P"-R-substituted fused thiophene moiety 24, while regioisomer 23 will not cyclize.
  • the fused thiophene moiety 24 can now be separated from uncylclized regioisomer 23, and can be decarboxylated to yield a'-hydro-P"-R-substituted fused thiophene moiety 25.
  • the methods described in the reaction schemes of FIGS. 2 and 3 can be used to make a variety of fused thiophene compounds.
  • the a- hydro-P-bromo thiophene moiety 11 of the reaction scheme of FIG. 2 is an a-hydro- ⁇ - bromo-P'-R'-substituted thiophene moiety 13
  • the end product fused thiophene will be a P"-R-substituted-P'-R'-substituted fused thiophene moiety 15.
  • R' can be, for example, an alkyl group having at least four carbons, and can be the same as or different from R.
  • R' can also be any other desired substitution, including an alkyl group having less than four carbons.
  • the general cyclization method of the reaction scheme of FIG. 2 can be used to simultaneously perform cyclization on both sides of a thiophene moiety, as shown in the reaction scheme of FIG. 4.
  • An a,a'-dihydro-P,P'-dibromo thiophene moiety 26 is used as the starting material. While in the reaction scheme of FIG.
  • thiophene moiety 26 is shown as a monocyclic simple thiophene, the skilled artisan will understand that thiophene moiety 26 can have fused thiophenes (such as thieno[3,2-Z?]thiophene or bisdithieno[3,2-Z?:2'-3'- ⁇ i]thiophene) as its fused thiophene ring system.
  • fused thiophenes such as thieno[3,2-Z?]thiophene or bisdithieno[3,2-Z?:2'-3'- ⁇ i]thiophene
  • Thiophene moiety 26 is acylated (for example, as described above using Friedel-Crafts chemistry) at both the a and a' positions, and is reacted with a 2-mercaptoacetate at both the ⁇ and ⁇ ' positions to yield an a,a'-bis(R-acyl)- P,PM)is(carboxymethylthio) thiophene moiety 27, which is cyclized (forming 28) and decarboxylated to form ⁇ ", ⁇ "'-bis(R-substituted) fused thiophene moiety 29, which has a fused thiophene ring system that is two rings larger than that of the starting material thiophene moiety 26.
  • the a,a'-dihydro ⁇ '-dibromo thiophene moiety 26 can be subjected to a first series of R-acylation/reaction with 2- mercaptoacetate/cyclization/decarboxylation reactions, then to a second series of reactions with a different R' group in the acylation step to provide a "-(R-substituted)- P"'-(R'- Su bstituted) fused thiophene moiety in which R and R' are different from one another.
  • the reaction scheme of FIG. 5 shows an alternative way to make an a,a'-bis(R- acyl) ⁇ '-bis(carboxymethylthio) thiophene moiety 27.
  • An ⁇ , ⁇ ', ⁇ , ⁇ '-tetrabromo thiophene moiety 30 is lithiated (selectively at the a-positions) and reacted with an aldehyde RCHO to form diol 31, which is oxidized to form a,a'-bis(R-acyl) ⁇ '- dibromo thiophene moiety 32, which is reacted with a 2-mercaptoacetate to form the ⁇ , ⁇ '-bis(R-acyl)- ⁇ , ⁇ '-bis(carboxymethylthio) thiophene moiety 27.
  • Fused thiophene moieties having relatively large fused thiophene ring systems can be synthesized using the reaction schemes described above. It is also possible to build large fused thiophene ring systems using the coupling and ring closure steps shown in the reaction scheme of FIG. 6.
  • a P-R-substituted-P'-bromo thiophene moiety 33, in which R is an alkyl group, is used as the starting material in this scheme; synthetic routes to 33 are described below.
  • the P-R-substituted-P'-bromo thiophene moiety 33 is shown as having a thieno[3,2- Z?]thiophene ring system, it may also have a monocyclic thiophene, or a larger fused thiophene ring system as described above at its core.
  • the P-R-substituted-P'-bromo thiophene moiety 33 is lithiated and reacted with sulfur bis(phenylsulfonate) (or sulfur dichloride) to form coupled thioether 34, which is lithiated and subjected to oxidative ring closure using Q1Q2 to form the P,P" disubstituted fused thiophene moiety 35.
  • Polycyclic P-R-substituted-P'-bromo thiophene moieties can be made by performing the reaction series of FIG. 2 on a P'-bromo thiophene moiety, as shown in the reaction scheme of FIG. 7.
  • Tetrabromothiophene is dilithiated (selectively at the expositions) and protonated to yield dibromothiophene 37, which is acylated (giving 38) and reacted with a 2-mercaptoacetate to give a-(R-acyl)-P-carboxymethylthio-P'- bromo thiophene moiety 39, which is cyclized and decarboxylated to yield 33.
  • the starting material in the reaction scheme of FIG. 7 is a monocyclic thiophene
  • polycyclic fused thiophene starting materials can be used as well.
  • P-R-substituted-P'-bromo thiophene compounds in which R is an alkyl group as defined herein.
  • R is an alkyl group as defined herein.
  • compounds described herein include those having structure 40, below.
  • R can be, for example, an unsubstituted alkyl group.
  • the unsubstituted alkyl group according to this aspect can be a straight-chain alkyl group (e.g. butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or hexadecyl), a branched alkyl group (e.g. sec-butyl, neo-pentyl, 4-methylpentyl), or a substituted or unsubstituted cycloalkyl group (e.g. cyclopentyl, cyclohexyl).
  • a straight-chain alkyl group e.g. butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or hexadecyl
  • a branched alkyl group e.g. sec-
  • R can be an alkyl group at least seven, at least eight, at least nine, or at least ten carbons in size, which is substituted or unsubstituted.
  • the substitution of the alkyl group is separated from the fused thiophene ring system by at least two carbons.
  • substituted alkyl groups according to this aspect include 6- hydroxyhexyl and 3-phenylbutyl.
  • the selection of R ⁇ and R2 moieties depends upon the end use of the fused thiophene moiety-containing composition. Any functionality on the substituted alkyl group can be protected in order to survive subsequent reaction steps.
  • R can be an alkyl group having at least six carbons in size.
  • alkyl groups for improving solubility include CkH 2 k+i, where k is an integer greater than or equal to six.
  • compounds having structure 40 above can be synthesized from ⁇ - R-substituted thiophene moieties by the bromination/debromination method shown in FIG. 8.
  • ⁇ -R-substituted thiophene 41 is fully brominated with molecular bromine to yield the tribrominated compound 42, which is selectively lithiated and protonated at the a-positions to yield the desired P-R-substituted-P'-bromo thiophene 40.
  • the method of FIG. 8 can also be used to make ⁇ -brominated fused thiophene moieties from fused thiophene moieties.
  • the monocyclic P-R-substituted-P'-bromo thiophene 40 can be used to make tricyclic bis(R-substituted) fused thiophene moieties according to the reaction scheme shown in FIG. 6.
  • the monocyclic P-R-substituted-P'-bromo thiophene 40 can also be used to make monosubstituted fused thiophene moieties according to the reaction scheme shown in FIG. 9.
  • monocyclic thiophene 40 is lithiated and reacted with formylpiperidine, and the adduct is hydrolyzed to yield aldehyde 43, which is reacted with a 2-mercaptoacetate, cyclized and decarboxylated to yield P-R-substituted fused thiophene 14.
  • the oxidized fused thiophene compounds and moieties described herein, for example 44 and 45, can be prepared by oxidation of the prepared fused thiophene compounds, for example, with MCPBA. Oxidation is generally selective at the central- most rings of the polycyclic fused thiophene ring systems; however, it is contemplated that any of the sulfur atoms in the fused thiophenes can be oxidized.
  • compounds comprising the moiety 3' or 4' can be produced by reacting a compound comprising the formula 210 or 220
  • n is an integer greater than or equal to one; in some embodiments, n is an integer of two or more; m is an integer greater than or equal to one; Ri and R2 are, independently, hydrogen or an alkyl group, wherein at least one of Ri and R2 is an alkyl group, with a compound having the formula (R 5 ) 3 Sn-Ar-Sn(R 5 )3, wherein Ar comprises an aryl group and R 5 is an alkyl group.
  • the dibromo-fused thiophene is coupled with a bis-stannyl aryl group.
  • the coupling reaction is generally performed in the presence of a catalysts such as, for example Pd(0).
  • the dibromo-fused thiophene may then be sequentially reacted with butyllithium and trimethyltinchloride to form the bis-tin- substituted fused thiophene as shown in FIG. 20.
  • the formation of the dipyrrolopyrole moiety can be done via the reaction scheme shown in Tieke et at, Beilstein, J. ORG. CHEM. 830 (2010), herein incorporated by reference in its entirety, and is described in FIG. 21 for example compound 3,6-bis(5-bromothiophen-2-yl)-2,5- diheptadecylpyrrolo[3,4-c]pyrrole-l,4(2H,5H)-dione.
  • the fused thiophene moiety and the dipyrrolopyrrole moiety may be combined to form 3" or 4" via any standard coupling reaction.
  • the fused thiophene moiety and the dipyrrolopyrrole moiety may be combined via a Stille-type coupling reaction as shown in FIG. 22.
  • fused thiophene compounds comprising the moieties 300 or 301 can be produced through a series of synthetic steps.
  • the fused thiophene core may be synthesized and brominated as described herein.
  • the dibromo-fused thiophene may then be reacted with a tributylstannyl compound in a Stille-type reaction in the presence of palladium catalyst to give the aryl-containing polymers.
  • the fused thiophene core may be reacted sequentially with butyllithium and trimethyltinchloride to form the bis-tin-substituted fused thiophene, which may be subsequently reacted with a brominated aryl moiety in a Stille-type reaction to form the conjugated polymer (FIG. 25).
  • the reaction in FIG. 25 uses palladium(O) catalyst as it showed good reliability, but palladium(II) based catalysts may also be used.
  • Fused thiophene and oxidized fused thiophene oligomers and polymers can be prepared using methodologies similar to those used in making oligo- and poly(thiophenes) described above.
  • ⁇ , ⁇ '-dihydro fused thiophene moieties can be oxidatively oligomerized or polymerized using iron (III) compounds (e.g., FeCi3, Fe(acac)s), or can be brominated and coupled in an organomagnesium mediated reaction.
  • fused thiophene moieties and oxidized fused thiophene moieties described herein can be incorporated into other conjugated polymers such as, for example phenylene, vinylene, and acetylene copolymers, using coupling reactions familiar to the skilled artisan.
  • the fused thiophene moieties and oxidized fused thiophene moieties described herein can be incorporated into other main chain and side chain polymers using techniques known in the art. It is contemplated that the fused thiophene compound can be oxidized prior to incorporation into an oligomer or polymer. In the alternative, the fused thiophene compound can be incorporated into the oligomer or polymer followed by oxidation.
  • reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
  • the organic component is extracted with ethyl acetate (3 x 100 mL) and the combined organic extracts are washed with brine (2 x 100 mL) and then water (100 mL).
  • the solvent is removed by evaporation, and the residue is dissolved in tetrahydrofuran (300 mL), forming a solution to which lithium hydroxide (84 mL, 10% solution in water), methanol (50 mL) and a catalytic amount of tetrabutylammonium iodide are added.
  • the mixture is heated at reflux for 3 hours, after which time the solvent is removed by evaporation, and the residue acidified with concentrated HCl (aq) (50 mL).
  • the organic component is extracted with ethyl acetate (3 x 100 mL).
  • the combined organic layers are washed with brine (2 x 100 mL), then water (100 mL) and dried over MgS0 4 .
  • the compound 55 is separated from unreacted compound 54 using column chromatography (S1O 2 / 5% ethyl acetate in hexane with 20% ethyl acetate in hexane to fully elute the compound 55), providing pure compound 55 (30 g, 46.1% yield).
  • a mixture of compound 62 (14.6 g, 0.054 mol), copper powder (2.00 g), and quinoline (80 mL) is heated at about 260 °C in a Woods metal bath. When no further bubbles of C0 2 are detected (about 2 hours), the mixture is allowed to cool to room temperature, and hexane (200 mL) is added. The mixture is washed repeatedly with HCL (aq) (1-2 M) to remove the quinoline. The organic layer is dried over MgS04 and concentrated by evaporation.
  • Example 3 di-P-substituted dithieno [3,2-6:2 '-3 '- ⁇ ]thiophenes and di- ⁇ - substituted dithieno[3,2-6:2 '-3 '- ⁇ ]thiophene-4,4-dioxides.
  • a chromic acid solution is prepared by dissolving sodium dichromate dihydrate (100 g, 0.34 mol) in water (300 mL), then concentrated sulfuric acid (136 g) is added, and the resulting solution is diluted to 500 mL.
  • the chromic acid solution (260 mL) is added dropwise at room temperature to a solution of Compound 65 (80.0 g, 0.137 mol) mixed with acetone (300 mL). The mixture is stirred overnight, after which time considerable solid had formed in the reaction mixture.
  • the reaction scheme of FIG. 12 is also used to make 3,5- dihexyldithieno [3,2-b :2 ',3 '- ⁇ i]thiophene and 3 ,5-dihexyldithieno [3 ,2 -b :2 ',3 '- i/]thiophene-4,4-dioxide.
  • 3,7-Didecylthieno[3,2-Z?]thieno[2',3 ':4,5]thieno[2,3-i/]thiophene 70 is synthesized as shown in the reaction scheme of FIG. 13.
  • 2,3,4,5-tetrabromothieno[3,2-Z?]thiophene (71) is prepared according to Fuller et al, 1 J. CHEM. SOC, PERKIN TRANS, 3465 (1997), which is hereby incorporated herein by reference.
  • Butyllithium (70 mL, 0.175 mol, 2.5 M in hexanes) is added dropwise at - 78 °C to a mixture of compound 71 (40.0 g, 0.088 mol) in 300 mL dry THF. The resulting mixture is stirred another 10 to 20 minutes and undecyl aldehyde (30.0 g, 0.176 mol) is added dropwise. The mixture is allowed to warm to room temperature and stirred overnight. Water (20 mL) is added, and the solvent is removed by evaporation. The residue is mixed with hexane (300 mL) and the resultant solid is collected by filtration.
  • Compound 75 (13.5 g, 0.021mol) is mixed with copper powder (0.9 g) in quinoline (80 mL), and the mixture is heated to 250-260 °C in a Woods metal bath. When no further bubbles of carbon dioxide gas could be detected (about 2 hours), the mixture is allowed to cool to room temperature and hot hexane (400 mL) is added. This mixture is then repeatedly washed in HC1 (2N, 4 x 50 mL). The hexane is partially removed by evaporation, and the resultant solid is collected by filtration and re-crystallized from hexane to afford compound 70 (7.0 g, 60.6% yield), m.p.: 1 11.0-113.3 °C.
  • Example 5 Attempt to synthesize ⁇ -substituted thieno [2,3- ⁇
  • Fused thiophene polymers are made using the general procedure described below. This procedure is adapted from Andersson et ah, 27 MACROMOLECULES 6506 (1994), herein incorporated by reference in its entirety.
  • a monomeric ⁇ , ⁇ '-dihydro ⁇ , ⁇ '-dialkyl fused thiophene compound (10 mmol) is dissolved in 30 mL chlorobenzene.
  • a suspension of ferric chloride (2.5 mmol) in 20 mL chlorobenzene is added to the monomer solution over half an hour.
  • the mixture is allowed to stir for several (e.g. from 6 to 24) hours at room temperature. It may be desirable to heat the reaction mixture at 80-90 °C for several hours for fused thiophene compounds having larger (e.g. 4 or greater) numbers of rings in their fused ring system.
  • the reaction mixture is then precipitated from 500 mL 95:5 methanol: water.
  • the precipitate is collected by filtration, dissolved in toluene, boiled with concentrated ammonia (3 x 60 mL), and boiled with ethylenediaminetetraacetic acid (0.05 M in water, 2 x 50 mL).
  • the product polymer is precipitated from methanol (500 mL); filtered and dried under vacuum at 70-80 °C.
  • poly(3,6-dihexylthieno[2,3- ⁇ i]thiophene) (35% yield); poly(3,6-didecylthieno[2,3-i/]thiophene (90% yield); poly(3,7-didecylthieno[3,2- Z?]thieno[2',3':4,5]thieno[2,3-i/]thiophene) (80% yield); and poly(3,5- didecyldithieno[3,2-6:2',3 '-i/]thiophene-4,4-dioxide) (43% yield).
  • Example 7 - Synthesis 2-2, 3-3 and 4-4 dimer and 5 and 7 ring systems [00133] The synthesis of 2-2 and 3-3 dimers and 5 and 7 ring systems is depicted in FIG. 15.
  • Butyllithium (2.5 M in hexane, 15.6mL, 0.039mol) is added dropwise at 0 °C diisopropylamine (4.0g, 0.039mol) in dry THF (30 mL). The resulting mixture is kept at 0 °C for 15 minutes, then 3-bromo-6-decanylthienythiophene (81) (14. Og, 0.039 mol) dissolved in THF (-30 mL) is added dropwise as a THF solution (30 mL). This mixture is stirred at 0 °C for one hour before copper (II) chloride (6.3 g, 0.047 mol) is added. The dark brown mixture is stirred for an additional 12 hours at room temperature.
  • 86 can also be prepared by the cyclization of 88 with butyllithium and copper chloride.
  • FIGS. 16 and 17 The synthesis of three-ring and four-ring tetraalkylsubstituted thienothiophene dimers is depicted in FIGS. 16 and 17, respectively.
  • Butyllithium (4.5 mL, 0.01 1 mol) is added dropwise under argon at room temperature to a hexane solution of 2,3-didecanyldithieno[3,2-b:2',3 '-d]thiophene (94) (5.16 g, 0.01 1 mol) and ,N,N',N',-tetramethylethylenediamine (TMEDA) (1.25 g, 0.011 mol). The resulting mixture is refluxed for one hour before copper (II) chloride powder is added to the reaction and this mixture is then stirred overnight.
  • TEDA ,N,N',N',-tetramethylethylenediamine
  • 96 can also be prepared by the cyclization of 95 with butyllithium and bis(phenylsulfonyl)sulfide.
  • Butyllithium (2.5 M in hexane, 10.9 mL, 0.0273 mol) is added dropwise at 0 °C to a flask with diisopropylamine (2.76 g, 0.027 mol) in dry THF (100 mL). The resulting mixture is kept at 0 °C for 15 minutes.
  • 3-bromo-5-decanyl-dithieno[3,2-b:2',3'- d]thiophene (101) (11.33 g, 0.0273 mol) is dissolved into THF (60 mL) and added dropwise to the reaction. This mixture is kept at 0 °C for one hour before 1- formylpiperidine is added.
  • ethyl thioglycolate (2.52 g, 0.021 mol) is added dropwise at 60-70 °C. This mixture is stirred at this temperature overnight and after checking the GC/MS for reaction completion, the mixture is poured into water (500 mL). The solid formed from the water solution is removed by filtration. The solid is then washed with water (2 x 200 mL) and methanol (200 mL). GC/MS shows a single peak at 465. After drying in vacuo, the target compound is used without further purification. (8.0 g, 86% yield). m.p.: 59.4-62.0 °C.
  • the mixture is cooled to room temperature and poured into 30% HCl (aq) (300 mL).
  • the organic solution is extracted with hexane (150 mL) and washed with 10% HCl (aq) several times to remove the quinoline from the organic layer.
  • the organic layer is then dried over MgS0 4 . After removing the solvent, the residue is recrystallized from ethanol to produce 4.44 g of target compound (81.3% yield), m.p.: 88.3-89.6 °C.
  • 109 can be prepared by coupling 108 with butyllithium and copper chloride.
  • the cyclization of 109 to produce 110 can be accomplished by reacting 109 with butyllithium and bis(phenylsulfonyl)sulfide.
  • the toluene solution then is boiled with concentrated ammonia (3 x 60 mL) and then boiled twice with ethylenediaminetetraacetic acid (EDTA) (0.05 M in water) (2 x 50 mL).
  • EDTA ethylenediaminetetraacetic acid
  • the resulting toluene is slowly added dropwise to methanol (500 mL) to precipitate polymer. After filtration, the polymer is dried in vacuum oven (70-80 °C) overnight to give the product PDC6FT2 in 35% yield.
  • Poly-3,6-didecanyl-thieno[3,2-b]thiophene (PDC10FT2) can also be produced in a 90% yield using this method.
  • the method above may also be used to produce the polymers PDC10FT4 (80% yield) and PDC10FTS3 (43% yield)
  • the resulting mixture is heated to 150 °C under argon for 14 hours before being precipitated into methanol (400 mL).
  • the collected solid polymer is washed with acetone (lOOmL), then washed using acetone in a Soxhlet extractor.
  • the solid polymer then is dissolved in chlorobenzene (100 mL) and filtered through a glass filter. After evaporating most of the chlorobenzene, the polymer as shown below is precipitated from methanol (300 mL) again.
  • the red polymer powder is dried under vacuum to give 0.9 grams (90.1% yield).
  • Dipyrrolopyrole Moiety Synthesis The formation of the dipyrrolopyrole moiety can be done via the reaction scheme shown in Tieke et ah, Beilstein, J. ORG. CHEM. 830 (2010), herein incorporated by reference in its entirety, and is described in FIG. 21. Formation of the bromothienyl-DPP synthesis is based on literature procedures. See, e.g., Tamayo et al, 1 12 J. PHYS. CHEM. 15543-52 (2008) and Huo et al, 42 MACROMOLECULES 6564-71 (2009), both herein incorporated by reference in their entireties.
  • FIG. 21 shows the synthesis of a specific bromothienyl-DPP.
  • Thiophene- carbonitrile and diisopropyl succinate are combined to form a thiophene substituted DPP. This is done in tert-amyl alcohol, with a yield of 82%.
  • the basic thienyl DPP is then N-alkylated using a straight chain alkyl bromide, followed by a-bromination of the thiophene groups to make it suitable as a Stille coupling co-monomer.
  • the final material (bromothienyl-DC17DPP) is purified by recrystallization from chloroform. When bromothienyl-DC16DPP is used, the yield is -65% for the three steps.
  • potassium tert-butoxide (67.4 g, 0.60 mol) and tert-amyl alcohol (400 mL) are added to a nitrogen-protected oven-dried three-neck round-bottom flask equipped with a mechanical stirrer, a thermometer and a reflux condenser. The mixture is heated to 105 °C for 1.5 h and to this mixture is added 2- thiophenenitrile (55.2 g, 0.50 mol) and the stirring continued at 105 °C for 30 min.
  • a mixture of diisopropyl succinate (40.4 g, 0.20 mol) in tert-amyl alcohol (60 mL) is added dropwise over a period of 3 h with rapid stirring.
  • the mixture is then stirred at 105 °C for a further 2 h, then cooled to 50 °C, at which point a mixture of methanol (300 mL) and water (80 mL) is added.
  • the reaction mixture is heated at reflux for 45 min before cooling to room temperature.
  • the mixture is poured over 500 g of ice, then concentrated hydrochloric acid (35% aq) (150 mL) and methanol (750 mL) are added and the mixture is stirred for 45 min.
  • N-bromosuccinimide (6.33 g, 35.6 mmol) is added to a solution of 2,5- diheptadecyl-3,6-bis(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-l,4-dione (13.0 g) in chloroform (200 mL) pre-heated to 60 °C in a 1 L flask, wrapped in aluminum foil to exclude light. The reaction is monitored by TLC and stopped as soon as no more mono-brominated species is observed (approximately 30 min), by pouring into methanol (600 mL) stirring in an ice bath.
  • DPP-FT Synthesis The fused thiophene and diketopyrrolpyrrole moieties may be combined via any standard coupling reaction, such as a Stille coupling reaction. See He et al. 21 ADV. MATER. 2007-2022 (2009), hereby incorporated by reference in its entirety. As shown in FIG.
  • the reaction may be done under nitrogen.
  • the reaction vessel and cap are introduced into a nitrogen glovebox, where toluene (20 mL) is added and the cap affixed to the vessel.
  • the vessel is then removed from the glovebox and the reaction microwaved at 160 °C for 2 h.
  • the mixture is cooled to 50 °C before release from the microwave reactor, then poured into a stirring mixture of methanol and acetylacetone (200 mL + 200 mL).
  • Hydrochloric acid (2 mL, 35% aq) is added and the mixture stirred for 16 h.
  • the mixture is filtered and the polymer placed into a glass with glass frit Soxhlet thimble.
  • the polymer is filtered in a Soxhlet apparatus with acetone (250 mL) for 24 h, then hexanes (250 mL) for 24 h.
  • the polymer is then filtered in a Soxhlet apparatus in chloroform (250 mL).
  • the chloroform solution is poured into methanol (400 mL) with rapid stirring, followed by moderate stirring for 20 min.
  • Fused thiophene based polymers such as P2TDC17FT4 have an upper mobility for charge transport (holes). This theoretical (and practical) limit may be raised by changing the polymer structure, replacing the bithiophene moiety with the mobility enhancing functionalized DPP moiety.
  • the polymeric properties of PTDC16DPPTDC17FT4 are determined using standard testing methods. TGA measurements on the material show it is thermally stable up to 400 °C. (FIG. 23) The TGA shows that the combination of the DPP moiety with the FT moiety unexpectedly provides a co-polymer that is highly stable relative to the DPP alone.
  • the color of the new PTDC 16DPPTDC 17FT4 polymer is a very dark green, almost black, indicating a broad absorption across the visible region of the solar spectrum.
  • UV-visible spectroscopy of both chloroform solution and thin film solid state spun from chloroform show a broad absorption from around 550 nm to around 950 nm and also a less intense absorption from around 300 nm to 500 nm (FIG. 24). This covers a very broad swath of the visible region and gives the polymer its dark green almost black appearance.
  • One advantage of this material is its use in photovoltaic devices, where such broad solar absorption is desirable.
  • the extension of the absorption so far out into the IR is also highly desirable and is an unusual property when combined with absorptions as low at 300 nm in the same molecule.
  • the strong light interaction also makes this material a suitable candidate for other optical and/or optoelectronic applications.
  • compounds of structure PTDC16DPPTDC17FT4 show a hole mobility of greater than 2 cm 2 /V-s, an on/off ratio of greater than 10 6 and a threshold voltage less than 2 V.
  • Example 12 Aryl-Linked Fused Thiophene Structure
  • Poly[(3,7-diheptadecylthieno[3,2-b]thieno[2',3' :4,5]thieno[2,3- d]thiophene-2,6-diyl)(2,l,3-benzothiadiazole-4,7-diyl)] ("P2BTDC17FT4") (FIG.

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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  • Electroluminescent Light Sources (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne des compositions comprenant des composés organiques hétérocycliques à base de composés thiophènes fusionnés, des polymères à base de composés thiophènes fusionnés et des procédés de fabrication des monomères et du polymère conjointement avec des utilisations dans des dispositifs à base de couche mince et autres dispositifs.
EP12845124.2A 2011-10-31 2012-10-31 Thiophènes fusionnés, procédés de fabrication de thiophènes fusionnés et leurs utilisations Withdrawn EP2773687A4 (fr)

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US8846855B2 (en) * 2011-10-31 2014-09-30 Corning Incorporated Conjugated fused thiophenes, methods of making conjugated fused thiophenes, and uses thereof
CN104703685B (zh) * 2012-08-27 2017-03-15 康宁股份有限公司 半导体稠合噻吩聚合物油墨制剂
JPWO2014132938A1 (ja) * 2013-02-28 2017-02-02 株式会社村田製作所 半導体装置およびｅｓｄ保護デバイス
US20170166690A1 (en) * 2013-11-27 2017-06-15 Corning Incorporated Advanced flow reactor synthesis of semiconducting polymers
JP6321978B2 (ja) * 2014-01-27 2018-05-09 富士フイルム株式会社 有機薄膜トランジスタ、有機半導体薄膜および有機半導体材料
US9580556B2 (en) * 2015-01-29 2017-02-28 Corning Incorporated DPP with branched alkyl-chain or (and) fused thiophene with branched alkyl-chain and the related designing strategy to increase the molecular weight of their semi-conducting copolymers
CN105924446A (zh) * 2016-04-27 2016-09-07 扬州鑫晶光伏科技有限公司 一种有机光伏材料及其制备方法
CN105884795A (zh) * 2016-04-27 2016-08-24 扬州鑫晶光伏科技有限公司 一种含噻吩环的有机光伏材料及其制备方法
TW201813995A (zh) * 2016-09-16 2018-04-16 美商康寧公司 稠合噻吩芳基噻二唑聚合物、該聚合物之製作方法，及其用途
CN111138810B (zh) * 2018-11-05 2024-05-17 康宁股份有限公司 用于有机薄膜晶体管的可uv图案化的聚合物掺混物
CN111752105A (zh) * 2019-03-27 2020-10-09 康宁股份有限公司 用于有机薄膜晶体管的可光图案化的杂型有机半导体聚合物
CN111057087B (zh) * 2019-11-01 2021-06-04 河南大学 一种非对称噻吩[7]螺烯同分异构体及其制备方法和应用

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US7838623B2 (en) * 2004-09-14 2010-11-23 Corning Incorporated Fused thiophenes, methods for making fused thiophenes, and uses thereof
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