JP2015502921A - Fused thiophene, method for producing condensed thiophene, and use thereof - Google Patents

Abstract

Described herein are compositions comprising heterocyclic organic compounds based on fused thiophene compounds, polymers based on fused thiophene compounds, and methods for making the monomers and polymers, and use in thin film-based devices and other devices.

Description

priority

  This application is subject to 35 USC §35, US Provisional Patent Application No. 61/553326, filed Oct. 31, 2011, the contents of which are relied upon and incorporated herein in its entirety. Claims the benefits of priority.

  Compositions comprising heterocyclic organic compounds are described herein. More particularly, fused thiophene compounds, methods for their preparation, and their use are described herein.

  Highly conjugated organic materials are currently the focus of large-scale research activities, mainly due to their interesting electronic and optoelectronic properties. These materials include field effect transistors (FETs), thin film transistors (TFTs), organic light emitting diodes (OLEDs), electro-optic (EO) applications, conductive materials, two-photon mixed materials, organic semiconductors, and nonlinear optics (NLO). ) Researched for use in a wide variety of applications, including as a material. Highly conjugated organic materials will find use in devices such as RFID tags, electroluminescent devices in flat panel displays, and photovoltaic and sensor devices.

Materials such as pentacene, poly (thiophene), poly (thiophene-co-vinylene), poly (p-phenylene-co-vinylene) and oligo (3-hexylthiophene) are used for various electronic and optoelectronic applications. It has been thoroughly researched. Most recently, condensed thiophene compounds have been found to have beneficial properties. For example, bisdithieno [3,2-b: 2 ′, 3′-d] thiophene (1, j = 2) has been found to efficiently π-stack in the solid state and has a high mobility (0.05 cm ² / V.s) and a high on / off ratio (up to 10 ⁸ ). Oligo- or poly (thieno [3,2-b] thiophene) (2) and oligo- or poly (dithieno [3,2-b: 2 ′,-3′-d] thiophene) (1)

Condensed thiophene oligomers and polymers such as have also been proposed for use in electronic and optoelectronic devices and have been shown to have acceptable conductive and nonlinear optical properties.

  However, unsubstituted condensed thiophene-based materials tend to have the disadvantages of low solubility, poor processability and unstable properties against oxidation. Therefore, there remains a need for fused thiophene-based materials that have acceptable solubility, processability and oxidative stability.

  Described herein are compositions comprising heterocyclic organic compounds such as fused thiophene compounds, methods of making them, and uses thereof. The compositions and methods described herein have a number of advantages over prior art compositions and methods. For example, the fused thiophene compositions described herein can be made more stable and processable than similar unsubstituted thiophene compositions. The polymers and oligomers containing fused thiophene moieties described herein can be made processably using conventional spin coating operations. Further, the compositions described herein can be made to be substantially free of β-H content and significantly improve the oxidative stability of the composition.

The first aspect is the formula 3 ″ or 4 ″:

Wherein m is an integer greater than 0; n is 1 or greater; X and Y are independently a covalent bond or aryl; R ₁ and R ₂ 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 R ₄ are independently substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, amino, Ester, aldehyde, hydroxyl, alkoxy, thiol, thioal Le, halides, acyl halides, there acrylates or vinyl ethers,; A and B are independently either S or O.

In some embodiments, A and B are O. In some embodiments, A and B are S. In some embodiments, at least one of R ₁ and R ₂ includes a substituted or unsubstituted alkyl. In some embodiments, at least one of R ₁ and R ₂ includes unsubstituted alkyl. In some embodiments, at least one of R ₃ and R ₄ includes a substituted or unsubstituted alkyl. In some embodiments, at least one of R ₃ and R ₄ includes a substituted or unsubstituted alkyl having at least 6 carbon atoms. In some embodiments, in some embodiments, n is 1-15. In some embodiments, the compound is included in a conjugated condensed thiophene polymer or oligomer where m> 1. In some embodiments, the compound comprises a polymer. In some embodiments, the polymer has a molecular weight of about 4000 to about 180,000 Da. In some embodiments, the polymer has a molecular weight of about 15,000 to about 50,000 Da. In some embodiments, the polymer has a molecular weight of about 20,000 to about 40,000 Da.

  Additional features and advantages are set forth in the following detailed description, some of which will be readily apparent to those skilled in the art from the description, or the written description and claims, and appended It will be appreciated by implementing the embodiments described in the drawings.

  It will be understood that the foregoing general description and the following detailed description are exemplary only and are intended to provide an overview or skeleton for understanding the nature and features of the present invention.

The accompanying drawings are included to provide a further understanding of this description, and are incorporated in and constitute a part of this specification. The drawings are not necessarily drawn to scale, and the sizes of the various elements may be distorted for clarity. The drawings illustrate one or more embodiments and, together with the description, serve to explain the principles and operation of the embodiments.
Reaction scheme showing a method for producing a β ″ -R-substituted fused thiophene moiety Reaction scheme showing a method for producing an α- (R-acyl) -β-carboxymethylthiothiophene moiety Reaction scheme showing a process for preparing α′-hydro-β ″ -R-substituted fused thiophene moieties Reaction scheme with simultaneous cyclization on both sides of the thiophene moiety Reaction scheme showing another method for preparing α, α′-bis (R-acyl) -β, β′-bis (carboxymethylthio) thiophene moieties Reaction scheme showing a method for producing 5-ring fused thiophene Reaction scheme showing a method for producing a polycyclic β-R-substituted-β′-bromothiophene moiety Reaction scheme showing a method for producing a β-R-substituted-β'-bromothiophene moiety Reaction scheme showing a method for producing mono-substituted fused thiophene moieties Reaction scheme showing the synthesis of 3,6-dihexylthieno [3,2-b] thiophene and 3,6-didecylthieno [3,2-b] thiophene according to Example 1 Reaction scheme showing the synthesis of 3-hexylthieno [3,2-b] thiophene according to Example 2 Reaction scheme showing the synthesis of 3,6-didecylthieno [3,2-b] thiophene and 3,6-didecylthieno [3,2-b] thiophene-4,4-dioxide according to Example 3 Reaction scheme showing the synthesis of 3,7-didecylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene according to Example 4 Reaction scheme showing failure to synthesize β-hexyl-substituted thieno [2,3-d] thiophene by conventional methodology as described in Example 5 Reaction scheme for synthesis of 2-2 dimer and pentacyclic system according to Example 7 Reaction scheme for the synthesis of 3-3 dimer and 7 ring system according to Example 7 Reaction scheme for the synthesis of a 7-ring tetraalkyl-substituted thienothiophene according to Example 8. Reaction scheme for the synthesis of 9-ring tetraalkyl-substituted thienothiophenes according to Example 8. Reaction scheme for producing fused thiophene copolymers Structures of various condensed thiophene copolymers produced by the methods described herein Structures of various condensed thiophene copolymers produced by the methods described herein Reaction scheme for forming bis-tin-substituted FT4 from dibromo-FT4 by continuous reaction with butyllithium and trimethyltin chloride Reaction scheme for preparing bis-bromothienyl-DC17DPP (diketopyrrolopyrrole = “DPP”) Reaction scheme for coupling bis-tin-substituted FT4 (FT4 = 4-ring fused thiophene) to bis-bromothienyl-DC17DPP by Stille type coupling with palladium catalyst 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] (“PTDC16DPPTDC17FT4” ) Graph showing that the material was thermally stable to temperatures above 400 ° C. This indicates the stability of the polymer. The graph which shows the UV-visible spectrum of the chloroform solution and solid film of PTDC16DPPTDC17FT4 polymer. Both species show a broad absorption from about 550 nm to about 950 nm and a weak absorption around 300 to 500 nm. These absorptions give the polymer a dark, almost green-black appearance, which may be useful for photovoltaic systems. Reaction scheme for forming a conjugated polymer comprising FT4 coupled by 4,7-benzo [c] -1,2,5-thiazole

  Prior to disclosing and describing the materials, articles and / or methods of the present invention, it is to be understood that the embodiments described below are not limited to particular compounds, synthetic methods, or uses, and may, of course, vary. Should be understood. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

  In this specification and in the claims that follow, a number of terms will be referred to that have the following meanings.

  Throughout this specification, unless the context requires otherwise, the word “comprise” or variations such as “comprises” and “comprising” are the integers listed. It will be understood that it may mean the inclusion of a process or integer or group of steps, but not any other integer or exclusion of a process or integer or group of processes.

  It should be noted that as used in the specification and the appended claims, the singular forms include the plural unless the context clearly dictates otherwise. Thus, for example, reference to “a pharmaceutical carrier” includes a mixture of two or more such carriers, and the like.

  “Optional” or “as appropriate” means that the event or situation described thereafter may or may not occur, and that the statement did or did not occur Means to include cases.

  Ranges may be expressed herein as “about” one particular value and / or “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, by use of the antecedent “about,” it will be understood that when a value is expressed as an approximation, that particular value forms another aspect. Furthermore, it will be further understood that each endpoint of those ranges is significant both with respect to the other endpoint and regardless of the other endpoint.

  The weight percentage of a component is based on the total weight of the formulation or composition in which the component is included, unless specifically stated otherwise.

  The term “alkyl group” as used herein refers to 1 to 40 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, or tetradecyl. Or a branched or unbranched saturated hydrocarbon group. This alkyl group can be substituted or unsubstituted. The term “unsubstituted alkyl group” is defined herein as an alkyl group consisting solely of carbon and hydrogen. The term “substituted alkyl group” refers to one or more hydrogen atoms, including but not limited to aryl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, amino groups, esters, aldehydes, hydroxyl groups, Defined herein as an alkoxy group substituted by an alkoxy group, a thiol group, a thioalkyl group, or a group comprising a halide, acyl halide, acrylate, or vinyl ether. For example, the alkyl group can be an alkylhydroxy group in which any hydrogen atom of the alkyl group is replaced by a hydroxyl group.

  The term “alkyl group” as defined herein also includes cycloalkyl groups. The term “cycloalkyl group” as used herein is a non-aromatic carbon-based ring of at least 3 carbon atoms, and in some embodiments, 3 to 20 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The term cycloalkyl group also includes heterocycloalkyl groups in which at least one of the ring carbon atoms is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.

  The term “aryl group” used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, and the like. The term “aryl group” also includes “heteroaryl groups” which mean aromatic rings consisting of at least three carbon atoms with at least one heteroatom contained 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 includes, but is not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy as defined herein. It can be substituted by more than one group. In some embodiments, the term “aryl group” is limited to substituted or unsubstituted aryl and heteroaryl rings having from 3 to 30 carbon atoms.

  The term “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.

  The term “alkenyl group” is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms whose structural formula contains at least one carbon-carbon double bond.

  The term “alkynyl group” is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms, whose structural formula contains at least one carbon-carbon triple bond.

  The term “conjugated group” can be described as the p-orbitals of the atoms of the group being connected through electron delocalization and the structure containing alternating single and double or triple bonds. Defined as a linear, branched or cyclic group, or a combination thereof, which may further contain a lone pair, radical, or carbenium ion. Conjugated cyclic groups may include both aromatic and non-aromatic groups, and may include polycyclic or heterocyclic groups such as diketopyrrolopyrrole. Ideally, the conjugated groups are attached in such a way as to continue conjugation between the thiophene moieties to which they are attached. In some embodiments, “conjugated groups” are limited to conjugated groups having 3 to 30 carbon atoms.

  Disclosed are compounds, compositions, and ingredients that can be used for the disclosed methods and compositions, can be used in combination therewith, can be used in their preparation, or are their products. Where these and other materials are disclosed herein and combinations, subsets, interactions, groups, etc. of these materials are disclosed, each of the various individual combinations and collection combinations and permutations of these compounds It is to be understood that specific references may not be explicitly disclosed, and each is specifically contemplated and described herein. Therefore, if the classes of molecules A, B and C and the classification of molecules D, E and F are disclosed and examples of combinatorial molecules AD are disclosed, each may not be listed individually, Each can be considered individually and collectively. Therefore, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, CE and C-F are specifically considered and A , B and C; D, E and F; and exemplary combinations AD are to be considered disclosed. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the subgroups AE, BF and CE are specifically contemplated and disclosed from the disclosure of exemplary combinations AD, A, B and C; D, E and F; Should be considered. This concept applies to all aspects of this disclosure including, but not limited to, steps of methods of making and using the disclosed compositions. Thus, if there are various additional steps that can be performed, each of these additional steps can be performed in any particular embodiment or combination of embodiments of the disclosed method, and so on. It will be understood that each of the combinations should be considered specifically and disclosed.

In one embodiment, Formula 3 or 4

Described herein are compositions comprising at least one fused thiophene moiety having:

In another embodiment, the formula 3 ′ or 4 ′

A composition comprising at least one moiety having: wherein n is an integer greater than zero; in some embodiments, n is an integer greater than or equal to 2; m is an integer greater than zero; In such embodiments, m is an integer greater than or equal to 2; o is an integer greater than zero; x is an integer greater than or equal to ₁ ; R ₁ and R ₂ are independently hydrogen or an alkyl group And at least one of R ₁ and R ₂ is an alkyl group, Ar is an aryl group, and n is not 1.

In one embodiment, for structures 3, 3 ′, 4, and 4 ′, n is an integer greater than zero; m is an integer greater than zero; R ₁ and R ₂ are independently hydrogen or alkyl And at least one of R ₁ and R ₂ is an alkyl group. As used herein, the fused thiophene ring system of the fused thiophene moiety is the heterocyclic core of that part, and the α and β substituents (eg, R ₁ and R ₂ ) attached to the fused thiophene ring system are Not included. For example, the fused thiophene ring systems of structures 3 and 4 having n = 1 are shown below as structures 5 and 6, respectively.

  The fused thiophene moiety described herein can have any number of fused rings. For example, the fused thiophene moiety can be bicyclic (3 and 3 ′, n = 1); tricyclic (4 and 4 ′, n = 1); tetracyclic (3 and 3 ′, n = 2); pentacyclic (4 And 4 ′, n = 2); six rings (3 and 3 ′, n = 3); or seven rings (4 and 4 ′, n = 3). The methods described herein allow the construction of fused thiophene moieties having any desired number of rings. In some embodiments, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, n is 2 or greater. In some embodiments, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, o is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. In some embodiments, the fused thiophene moiety can be three or more rings (ie, 4 or 4 ', n ≧ 1; or 3 or 3 ′, n ≧ 2). In some embodiments, the fused thiophene moiety can be four or more rings (ie, 4 or 4 ', n ≧ 2; or 3 or 3', n ≧ 2).

In another embodiment, the composition has formula 3 ″ or 4 ″

Wherein n is an integer greater than or equal to 1; m is an integer greater than or equal to 1; X and Y are independently a covalent bond or aryl; R ₁ and R ₂ is independently alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether; R ₃ And R ₄ are independently alkyl, alkenyl, alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hexyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether; A and B are German To be either S or O.

  The fused thiophene moieties described in 3 ″ and 4 ″ can have any number of fused rings greater than 3. For example, a fused thiophene moiety can be a four ring (3 ″, n = 2); a five ring (4 ″, n = 2); a six ring (3 ″, n = 3); or a seven ring (4 ″, n = 3). ). The method disclosed herein allows the construction of fused thiophene moieties having any desired number of rings. In one embodiment, for 3 ″ and 4 ″, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15.

The fused thiophene moiety described herein is substituted with an alkyl group at at least one of the β positions of the fused thiophene ring system. As used herein, the alpha position of the fused thiophene ring system is a non-fused carbon center directly adjacent to the sulfur of the fused thiophene, whereas the beta position is separated from the fused thiophene sulfur by the alpha position. Non-condensable carbon center. In structures 3, 3 ′, 3 ″, 4, 4 ′, and 4 ″, the α position is shown as being connected to the rest of the composition, whereas the β position is R ₁ and R Replaced by ₂ .

In one embodiment, at least one of R ₁ and R ₂ is an alkyl group. There has been no previous method for preparing fused thiophene moieties of structures 3, 3 ′, 3 ″, 4, 4 ′, and 4 ″ having an alkyl substituent at the β position of the fused thiophene ring system. As described in more detail in the examples below, the methods conventionally used to alkylate simple unfused thiophenes do not work when used in attempts to alkylate fused thiophene ring systems. In one embodiment, a method for producing a fused thiophene moiety having a large alkyl substituent at the β-position of a fused thiophene ring system is described herein.

In one embodiment, R ₁ and R ₂ can be a wide variety of substituted or unsubstituted alkyl groups. For example, at least one of R ₁ and R ₂ is an unsubstituted alkyl group. In this embodiment, the unsubstituted alkyl group is a straight chain alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or hexadecyl), branched alkyl group ( For example, it may be sec-butyl, neo-pentyl, 4-methylpentyl), or a substituted or unsubstituted cycloalkyl group (eg, cyclopentyl, cyclohexyl). In another embodiment, at least one of R ₁ and R ₂ is a substituted alkyl group that itself contains at least 4 carbons in size. In yet another embodiment, the alkyl group substitution is separated from the fused thiophene ring system by at least two carbons. R ₁ and / or R ₂ is an aryl group, a cycloalkyl group, an 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 halogen It may be substituted with a fluoride, acrylate, or vinyl ether. Examples of substituted alkyl groups include, but are not limited to, 6-hydroxyhexyl and 3-phenylbutyl. The choice of R ₁ and R ₂ depends on the end use of the composition containing the fused thiophene moiety. The methods described herein allow the synthesis of fused thiophene moieties with a wide variety of R ₁ and R ₂ substituents. Any functionality of the substituted alkyl group can be protected to survive subsequent reaction steps.

Unsubstituted fused thiophene ring systems (ie, no substituents at the α or β positions) tend to be relatively insoluble. Thus, in one embodiment, R ₁ and R ₂ can be an alkyl group having at least 6 carbons in size. For example, the alkyl group can have the formula C _k H _{2K + 1} , where k is an integer greater than or equal to 6.

In some embodiments, the fused thiophene ring system is substituted at both β positions, and thus there are no β hydrogens in the ring system. For example, in one embodiment, neither R ₁ nor R ₂ in structure 3, 3 ′, 3 ″, 4, 4 ′, and 4 ″ is H. Such moieties can be included in oligomers and polymers that are substantially free of beta hydrogen content and have increased oxidative stability. For example, the molar ratio of β hydrogen to the fused thiophene ring system can be less than about 1/6, 1/7, 1/8, 1/9, or 1/10. In yet another embodiment, one or both of R ₁ and R ₂ can be an alkyl group. In one embodiment, R ₁ and R ₂ are the same alkyl group. When R ₁ and R ₂ are the same, the regioregular polymer can be easily constructed because the problem of regioselectivity of the polymerization reaction (ie, head-to-head to head-to-head coupling) is eliminated. In other embodiments, R ₁ and R ₂ may be different. For example, R ₁ can be at least 4 carbons in size, and R ₂ is carbon less than 4 in size (eg, a methyl group). Alternatively, in another embodiment, both R ₁ and R ₂ can be at least 4 carbons in size.

  With respect to the moieties 3 ', 3 ", 4' and 4", an aryl group (Ar) is attached to the alpha position of the fused thiophene moiety.

In one embodiment, Ar comprises one or more unfused thiophene groups, one or more fused thiophene groups, or a combination of unfused and fused thiophene groups. For example, the fused thiophene moiety is of formula 200 or 201:

In which o is 1 or more; in some embodiments, o is 1, 2 or 3; R ₃ and R ₄ are independently hydrogen or an alkyl group. In some embodiments, n is 2, 3 or 4, and m is 1. In other embodiments, n is 2, 3 or 4, m is 1, and o is 1, 2 or 3. When Ar is a fused thiophene, it is believed that the fused thiophene can be one fused thiophene group or two or more fused thiophene groups. When Ar is two or more condensed thiophene groups, the condensed thiophene groups may be the same or different. For example, Ar can be a bis-fused thiophene covalently linked to a tris-fused thiophene. In other embodiments, Ar can be one or more substituted or unsubstituted thiophene groups attached to a substituted or unsubstituted fused thiophene group.

In another embodiment, with respect to moieties 3 ′, 3 ″, 4 ′ and 4 ″, the Ar moiety is 300 or 301

Wherein A and B are O or S, and R ₃ and R ₄ 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; X and Y are independently a covalent bond or one or more An aryl group, one of which is ultimately attached to the fused thiophene moiety.

In another embodiment, any of the sulfur atoms present in the fused thiophene compounds described herein can be oxidized to produce SO ₂ groups. In another embodiment, the composition comprises the following oxidized fused thiophene moiety:

At least one of the above. In some embodiments, for structures 44 and 45, n is an integer greater than zero; in some embodiments, n is an integer greater than or equal to 2; m is greater than or equal to ₁ ; and R ₁ and R ₂ is independently hydrogen or an alkyl group; each T is independently S or SO ₂ , and in at least one of the most central rings of the oxidized fused thiophene ring system, T is SO ₂ . Each T is independently S and SO ₂ , and in at least one of the most central rings of the oxidized fused thiophene ring system, T is SO ₂ . As used herein, the most central ring of a fused thiophene ring system having an odd number of 2q + 1 fused rings is the q + 1th ring from the end of the ring system. The most central rings of a fused thiophene ring system having an even 2q fused ring are the q-th and q + 1-th rings from the end of the ring system. For example, the most central ring in a 3-ring system is the second ring, the most central ring in the 4-ring system is the second and third rings, and the most central ring in the 5-ring system is the third ring. It is.

In another embodiment, the oxidized moiety is of formula 44 ′ or 45 ′:

Wherein in at least one of the central rings of the oxidized fused thiophene ring system, T is SO ₂ . In one embodiment, T in at least one of the most central rings is SO ₂ and the remaining S atoms are not oxidized.

Any of the oxidized fused thiophene compounds described herein can be used in the previously described polymers, oligomers, monomers, chromophores, and other compositions. For example, at least one oxidized condensed thiophene moiety may be present in the composition at a total concentration of at least 1% by weight. The value of n can be, for example, 1, 2, 3, 4, or 5. In other embodiments, the fused thiophene moiety can be three or more rings (ie, 45 ′, n ≧ 1; or 44 ′, n ≧ 2). In some embodiments, n is 2 or greater. In yet another embodiment, at least one of R ₁ and R ₂ is an alkyl group having a size of at least 6 carbons directly attached to the oxidized fused thiophene ring system core of the oxidized fused thiophene moiety. Both R ₁ and R ₂ can be alkyl groups and can be the same or different from each other. In some embodiments, neither R ₁ nor R ₂ is H. In other embodiments, the composition has a ratio of β hydrogen to oxidized fused thiophene ring system of less than about 1/10, 1/9, 1/8, 1/7, or 1/6. In one embodiment, the oxidized condensed compound has the structure:

Wherein n is an integer greater than zero; R ₁ and R ₂ are independently hydrogen or an alkyl group; Q is independently hydrogen, substituted or unsubstituted alkyl group , Acyl halides, esters, aldehydes, ketones, hydroxyl groups, thiol groups or alkyl-substituted thiol groups, alkoxy groups, acrylate groups, amino groups, vinyl ether groups, hydroxyl alkyl groups, carboxylic acid groups, or halides.

Examples of oxidized fused thiophene moieties are shown below as structures 46, 47, 48 and 49:

Condensed thiophene moieties of structures 3, 3 ′, 3 ″, 4, 4 ′, 4 ″, 44 ′, and 45 ′ may exist as simple monomer-fused thiophenes or are more complex such as oligomers and polymers It may be contained in any other compound. For example, the fused thiophene moieties described in 3 and 4 have formulas 7 and 8:

In which n is an integer greater than zero; in some embodiments, n is an integer greater than or equal to 2; and R ₁ and R ₂ are Is independently hydrogen or alkyl; Q is independently hydrogen, substituted or unsubstituted alkyl group (eg, alkylhydroxy group), carboxylic acid, acyl halide, ester, aldehyde, ketone, hydroxyl group A thiol group or an alkyl-substituted thiol group, an alkoxy group, an acrylate group, an amino group, a vinyl ether, or a halide. In one embodiment, each Q in 7 and 8 is bromide. In certain embodiments, monomers having structures 7 and 8 can be used to produce condensed thiophene oligomers and polymers, as described below.

  Condensed thiophene monomers 7 and 8, or alternatively oxidized condensed thiophene monomers 44 and 45, are included in oligomers and polymers with conjugated homo-oligomers or homopolymer blocks of fused thiophene moieties to provide condensed thiophene moieties 3, 3 Polymers having '3 ", 4, 4', or 4", or 44 'and 45' can be produced. For example, according to one embodiment, the oligomer or polymer comprises fused thiophenes of structure 3, 3 ′, 3 ″, 4, 4 ′, 4 ″, 44 ′ and 45 ′, where m is 1 Greater than. In yet another embodiment, m is at least about 4. In another embodiment, m is at least about 10 when the polymer is a homopolymer. In this embodiment, it is believed that monomers 7 or 8 (or alternatively 44 or 45) can be polymerized to produce a homopolymer consisting of residues having formula 3 or 4 (or alternatively 44 ′ or 45 ′). It is done. In other embodiments, m is 1 to 1,000, 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.

  In other embodiments, the fused thiophene monomers described herein (eg, 7 and 8) can be included in the conjugated copolymer along with other aromatic or unsaturated moieties. For example, fused thiophene monomers 7 and 8 (or alternatively 44 or 45) can be copolymerized with other substituted or unsubstituted fused thiophene moieties to form conjugated fused thiophene polymers or oligomers. Alternatively, the fused thiophene monomers 7 and 8 (44 or 45) can be copolymerized with substituted or unsubstituted thiophenes to form thiophene / fused thiophene polymers or oligomers. Fused thiophene monomers 7 and 8 (44 or 45) can be copolymerized with other moieties commonly used in conjugated polymers such as vinylene, phenylene, or other arylene or heteroarylene moieties.

The fused thiophene moieties described herein can be included in a wide variety of other types of polymers. For example, condensed thiophenes having the formulas 7 and 8 (44 or 45) are in the main chain of polymers such as, for example, polyesters, polyurethanes, polyethers, polyamides, polycarbonates or polyketones and, for example, polyacrylates, polymethacrylates, Alternatively, it can be included in the side chain of a polymer such as poly (vinyl ether). It is contemplated that fused thiophenes having formulas 7 and 8 (44 or 45) can be modified with reactive groups that allow the monomer to be included in the polymer (eg, acyl chloride, alcohol, acrylate, amine, vinyl ether). For example, R ₁ , R ₂ , and / or Q can be modified with such reactive groups.

  In other embodiments, the moieties 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ are homomonomers of the 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ moieties (ie, just One), conjugated homooligomers or homopolymer blocks can be included to produce the polymer. For example, according to one embodiment, the oligomer or polymer comprises fused thiophenes of structure 3 ', 3 ", 4', 4", 44 'and 45', where m is greater than 1. In yet another embodiment, m is at least about 4. In another embodiment, m is at least about 10 when the polymer is a homopolymer. In this embodiment, it is contemplated that the moieties 3 ', 3 ", 4', 4", 44 'and 45' can be polymerized to produce a homopolymer. In other embodiments, m is 1 to 1,000, 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.

  In some embodiments, a polymer having 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ portion conjugated homomonomers (ie, only one), homooligomer or homopolymer block is about 4 And a molecular weight of about 180,000 Da. In some embodiments, the polymer has a molecular weight of about 15,000 to about 50,000 Da. In some embodiments, the polymer has a molecular weight of about 20,000 to about 40,000 Da. In some embodiments, a polymer having 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ portion conjugated homomonomers (ie, only one), homooligomer or homopolymer block is about 4 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 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 5,000 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 12 5,000, 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 , 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 160,000, about 10,000 to about 140 , About 10,000 to about 120,000, about 10,000 to about 100,000, about 10,000 to about 80,000, about 10,000 to about 70,000, about 10,000 to about 60 , About 10,000 to about 50,000, about 10,000 to about 40,000, about 10,000 to about 30,000, about 20,000 to about 180,000, about 20,000 00 to about 160,000, about 20,000 to about 140,000, about 20,000 to about 120,000, about 20,000 to about 100,000, about 20,000 to about 80,000, about 20,000 000 to about 70,000, about 20,000 to about 60,000, about 20,000 to about 50,000, about 20,000 to about 40,000, about 20,000 to about 30,000, about 30,000 30,000 to about 180,000, about 30,000 to about 160,000, about 30,000 to about 140,000, about 30,000 to about 100,000, about 30,000 to about 80,000, about 30,000 000 to about 70,000, about 30,000 to about 60,000, about 13,000 to about 50,000, about 30,000 to about 40,000, about 50,000 To about 180,000, about 50,000 to about 160,000, about 50,000 to about 140,000, about 50,000 to about 120,000, about 50,000 to about 100,000, about 50,000 To about 80,000, about 50,000 to about 70,000, or about 50,000 to about 60,000 Da. In some embodiments, a polymer having 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ moieties of conjugated homomonomers (ie, only one), homooligomer or homopolymer block is 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 , 90,000, 100,000, 110,000, 120,000, 130,000, 140,000, 150,000, 160,000, 170,000, or 180,000 Da.

  In other embodiments, the moieties 3 ', 3 ", 4', 4", 44 'and 45' can be included in the conjugated copolymer along with other aromatic or unsaturated moieties. For example, moieties 3 ', 3 ", 4', 4", 44 'and 45' can be copolymerized with other substituted or unsubstituted fused thiophene moieties to form conjugated fused thiophene polymers or oligomers. Alternatively, moieties 3 ', 3 ", 4', 4", 44 'and 45' can be copolymerized with substituted or unsubstituted thiophenes to form thiophene / fused thiophene polymers or oligomers. Copolymerizing the moieties 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ with other moieties commonly used in conjugated polymers, such as vinylene, phenylene, or other arylene or heteroarylene moieties. There is no problem.

  The portions 3 ', 3 ", 4', 4", 44 'and 45' described herein can be included in a wide variety of other types of polymers. For example, the portions 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ are in the main chain of a polymer such as, for example, polyester, polyurethane, polyether, polyamide, polycarbonate, or polyketone, and for example poly It can be included in the side chain of a polymer such as acrylate, polymethacrylate, or poly (vinyl ether). Modify moieties 3 ′, 3 ″, 4 ′, 4 ″, 44 ′ and 45 ′ with reactive groups (eg acyl chlorides, alcohols, acrylates, amines, vinyl ethers) that allow the monomer to be included in the polymer. It is considered possible.

In another embodiment, the fused thiophenes described herein can be included in donor-acceptor chromophores, such as those commonly used in polymer electro-optic materials. For example, a fused thiophene moiety of structures 3 and 4 can be converted to structures 9 or 10:

In which D is an electron donating group and A is an electron withdrawing group. Donor-acceptor chromophores are more fully described in US Pat. Nos. 6,584,266, 6,514,434, 6,448,416, 6,444,830 and 6,393,190, each of which is hereby incorporated by reference. Have been described. In one embodiment, a fused thiophene having formula 7 or 8 can be reacted with an electron donating group and an electron withdrawing group to produce compounds having formulas 9 and 10, respectively.

  In various embodiments, the composition described herein is a condensed thiophene having a concentration of structures 3 or 4 (or 44 or 45) sufficiently high to produce the desired electronic or optoelectronic properties in the composition. Has a part. For example, the composition has at least one fused thiophene moiety of structure 3 or 4 (or alternatively 44 or 45) at a total concentration of at least 1% by weight. In yet another embodiment, the compositions described herein have at least one fused thiophene moiety of structure 3 or 4 (or 44 or 45) at a total concentration of at least 3% by weight. In an additional embodiment, the composition comprises structures 3 or 4 (or 44 or 45) at a higher total concentration, for example, at least 10%, 20%, 30%, 40%, or 50% by weight. Having at least one fused thiophene moiety. Because of the presence of an alkyl group at the β-position of the fused thiophene ring, the composition can have a higher concentration of fused thiophene moieties but is still soluble and remains processable.

  A wide variety of devices can be made using the compositions (monomers, oligomers, polymers) described herein. For example, the device can be a fused thiophene moiety-containing composition configured into an electronic, photoelectron, or non-linear optical device. The composition described here is a field effect transistor (FET), thin film transistor (TFT), organic light emitting diode (OLED), PLED application, electro-optic (EO) application, conductive material, two-photon mixed material, organic semiconductor And as non-linear optical (NLO) materials, as RFID tags, in electroluminescent devices in flat panel displays, in photovoltaic devices, as chemical or biological sensors. The compounds described herein may be used in the apparatus described in US Provisional Patent Application No. 61 / 567,342, which is hereby incorporated by reference in its entirety.

In some embodiments, the condensed thiophene-based polymer embodied herein has an unexpectedly high hole mobility, on / off ratio, or low threshold voltage when included in a thin film device. In some embodiments, wherein the hole mobility of the embodied fused thiophene-based ^{polymers, 0.5cm 2 / V · s,} 0.75cm 2 / V · s, 1.0cm 2 / V · ^{s, 1.25cm 2 / V · s} , 1.5cm 2 / V · s, 1.75cm 2 / V · s, 2.0cm 2 / V · s, 2.25cm 2 / V · s, 2.5cm ^{2 / V · s, 2.75cm 2} / V · s, 3.0cm 2 / V · s, 3.25cm 2 / V · s, 3.5cm 2 / V · s, 3.75cm 2 / V · s Or 4.0 cm ² / V · s, larger. In some embodiments, the condensed thiophene-based polymer embodied herein has an on / off ratio greater than 10 ⁵ , 10 ⁶ , 10 ⁷ , 10 ⁸ , 10 ⁹ , or 10 ¹⁰ . In some embodiments, the condensed thiophene-based polymers embodied herein are 0.25V, 0.5V, 0.75V, 1.0V, 1.25V, 1.5V, 1.75V, 2. Has a threshold voltage less than 0V, 2.25V, 2.5V, 2.75V, 3.0V, 3.25V, 3.5V, 3.75V, or 4.0V.

Polymers containing the fused thiophene moieties (3, 3 ′, 3 ″, 4, 4 ′, and 4 ″) described herein have improved packing ability and thermal stability. In some embodiments, the polymer also exhibits a liquid crystal phase over a specific temperature range. The liquid crystal characteristics can be easily adjusted by changing the lengths of the alkyl groups R ₁ and R ₂ . This polymer also has good solubility in organic solvents such as, for example, toluene, chlorobenzene, which allows thin film casting using techniques known in the art.

A method for producing the fused thiophene compound is also disclosed herein. In one embodiment, the method of making a β ″ -R-substituted fused thiophene moiety is:
(I) providing an α-hydro-β-bromothiophene moiety;
(Ii) acylating the α-hydro-β-bromothiophene moiety with an R-acyl moiety wherein the thiophene moiety is an alkyl group with R having at least 4 carbons in the α position. Converting to an acyl) -β-carboxymethylthiothiophene moiety;
(Iii) replacing β-bromide with 2-mercaptoacetate;
(Iv) cyclizing the α- (R-acyl) -β-carboxymethylthiothiophene moiety to form an α ″ -carboxy-β ″ -R-substituted fused thiophene moiety; and (v) the α ″- Removing the carboxylate from the carboxy-β ″ -R-substituted fused thiophene moiety to form a β ″ -R-substituted fused thiophene moiety;
It has.

In one embodiment, a method for making a β ″ -R-substituted fused thiophene compound is shown in the reaction scheme of FIG. 1. First, an α-hydro-β-bromothiophene moiety 11 is provided. The α-hydro-β-bromothiophene moiety 11 can be a simple uncondensed thiophene, as shown in Structures 12 and 13 below, where Structure 12 is an unsubstituted, uncondensed α-hydro- β-bromothiophene, which, upon ring condensation, produces thienothiophene 14 with one β substituent, structure 13 is R ′ substituted at the β ′ center (ie, α-hydro -Β-bromo-β'-R'-substituted thiophene), which produces a β-substituted thienothiophene 15 in two places upon ring condensation.

This α-hydro-β-bromothiophene is then converted to α- (R-acyl) -β-carboxymethylthiothiophene moiety 16. As used herein, the name “R-acyl” means to show the following radical structure 17 and the name “carboxymethylthio” means to show the following radical structure 18. Where Z is the carboxylate terminus (which may be, for example, H, substituted alkyl, unsubstituted alkyl). In some embodiments, Z is H, methyl, ethyl, or propyl. Using the reaction scheme shown in FIG. 2 and described in more detail in the Examples, the α-hydro-β-bromothiophene moiety 11 to the α- (R-acyl) -β-carboxymethylthiothiophene moiety 16 is used. Conversion can be performed. Initially, the α-hydro-β-bromothiophene moiety is acylated at the α-position with an R-acyl moiety using RCOCl and AlCl ₃ where R is an alkyl group having at least 4 carbons. This acylated product is reacted with ₂ -mercaptoacetate HSCH ₂ COOZ to produce the α- (R-acyl) -β-carboxymethylthiothiophene moiety 16. In the reaction scheme of FIG. 2, R-acylation is performed first, but in some cases the reaction can be performed in the opposite order.

  The α- (R-acyl) -β-carboxymethylthiothiophene moiety 16 is then cyclized (eg, by base-catalyzed condensation, often under the same conditions as the reaction with 2-mercaptoacetate) to produce α ″ -carboxy- A β ″ -R-substituted fused thiophene moiety 19 is produced from which the carboxylate is removed to form a β ″ -R-substituted fused thiophene moiety 20. R is an alkyl group having at least 4 carbons. .

  If the α-hydro-β-bromothiophene moiety 11 in the reaction scheme of FIG. 2 has a hydrogen at the α ′ position, the acylation step will not be specific for the α position. For example, as shown in the reaction scheme of FIG. 3, the α, α′-dihydro-β-bromothiophene moiety 21 is acylated and reacted with 2-mercaptoacetate to give the desired α- (R-acyl)- A mixture of products is formed comprising an α′-hydro-β-carboxymethylthiothiophene moiety 22 and an undesired regioisomeric α′-hydro-α- (R-acyl) -β-carboxymethylthiothiophene moiety 23. Since moieties 22 and 23 are likely to be separated from each other, the mixture can be subjected to a cyclization step; regioisomer 22 can be cyclized to form α′-hydro-α ″ -carboxy-β ″ -R-substituted fused thiophene. Whereas the portion 24 is formed, the regioisomer 23 is not cyclized. Here, the fused thiophene moiety 24 can be separated from the non-cyclized regioisomer 23 and the carboxylate can be removed to produce the α′-hydro-β ″ -R-substituted fused thiophene moiety 25. .

  In other embodiments, the methods described in the reaction schemes of FIGS. 2 and 3 can be used to produce a wide variety of fused thiophene compounds. For example, if the α-hydro-β-bromothiophene moiety 11 in the reaction scheme of FIG. 2 is an α-hydro-β-bromo-β′-R′-substituted thiophene moiety 13, the final product condensed thiophene is β "-R-substituted-β'-R'-substituted thiophene moiety 15. R 'can be, for example, an alkyl group having at least 4 carbons, and can be the same as or different from R. R ′ can be any other desired substituent, including alkyl groups having less than 4 carbons.

  Using the general cyclization method of the reaction scheme of FIG. 2, cyclization can be performed simultaneously on both sides of the thiophene moiety, as shown in the reaction scheme of FIG. The α, α'-dihydro-β, β'-dibromothiophene moiety 26 is used as the starting material. Although the α, α′-dihydro-β, β′-dibromothiophene moiety 26 is shown as a monocyclic simple thiophene in the reaction scheme of FIG. It will be appreciated that it is possible to have fused thiophenes (such as thieno [3,2-b] thiophene or bisdithieno [3,2-b: 2′-3′-d] thiophene) as the thiophene ring system. The thiophene moiety 26 is acylated at both the α and α ′ positions (eg, as described above using the Friedel-Crafts reaction) and α, α′-bis (R-acyl) -β, β. A '-bis (carboxymethylthio) thiophene moiety 27 is produced, which is cyclized (forms 28) and the carboxylate is removed to form a β ″, β ″ ′-bis (R-substituted) fused thiophene moiety 29. It has a fused thiophene ring system that is two rings larger than that of the starting thiophene portion 26. Alternatively, the α, α′-dihydro-β, β′-dibromothiophene moiety 26 is subjected to a first series of R-acylation / 2 reaction with 2-mercaptoacetate / cyclization / decarboxylate reaction, and then A β ″-(R-substituted) -β ″ ′-(R′-substituted) fused thiophene, wherein R and R ′ are different from each other by reacting with different R ′ groups in the second series of acylation steps You can provide the part.

  The reaction scheme of FIG. 5 shows another method for preparing α, α′-bis (R-acyl) -β, β′-bis (carboxymethylthio) thiophene moiety 27. The α, α ′, β, β′-tetrabromothiophene moiety 30 is lithiated (optionally at the α position) and reacted with the aldehyde RCHO to form the diol 31, which is oxidized to α, α′-bis (R-acyl) -β, β′-dibromothiophene moiety 32 is formed and reacted with 2-mercaptoacetate to form α, α′-bis (R-acyl) -β, β ′. -Forming the bis (carboxymethylthio) thiophene moiety 27;

Using the reaction scheme described above, a fused thiophene moiety having a relatively large fused thiophene ring system can be synthesized. It is also possible to construct large fused thiophene ring systems using the coupling and ring closure steps shown in the reaction scheme of FIG. The β-R-substituted-β′-bromothiophene moiety 33, where R is an alkyl group, is used as the starting material in this scheme; the synthetic route to 33 is described below. In the reaction scheme of FIG. 6, the β-R-substituted-β′-bromothiophene moiety 33 is shown to have a thieno [3,2-b] thiophene ring system, but with a monocyclic thiophene in its core, Or it may have a larger fused thiophene ring system as described above. The β-R-substituted-β′-bromothiophene moiety 33 is lithiated and reacted with bis (phenylsulfonic acid) sulfur (or sulfur dichloride) to form the coupled thioether 34, which is converted to lithium. And oxidative ring closure using CuCl ₂ to form the β, β ″ disubstituted fused thiophene moiety 35.

  The polycyclic β-R-substituted-β′-bromothiophene moiety is prepared by performing the series of reactions of FIG. 2 on the β′-bromothiophene moiety as shown in the reaction scheme of FIG. Can do. Tetrabromothiophene is dilithiated (optionally in the α position) and protonated to produce dibromothiophene 37, which is acylated (to produce 38) and reacted with 2-mercaptoacetate, The α- (R-acyl) -β-carboxymethylthio-β′-bromothiophene moiety 39 is produced, which is cyclized to remove the carboxylate to produce 33. Although the starting material in the reaction scheme of FIG. 7 is a monocyclic thiophene, polycyclic fused thiophene starting materials can be used as well.

In another embodiment, described herein are β-R-substituted-β′-bromothiophene compounds, wherein R is an alkyl group as defined herein. For example, some of the compounds described herein have the following structure 40: R can be, for example, an unsubstituted alkyl group.

Unsubstituted alkyl groups according to this embodiment include straight chain alkyl groups (eg, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or hexadecyl), branched chain alkyls (eg, sec-butyl, neo- Pentyl, 4-methylpentyl), or a substituted or unsubstituted cycloalkyl group (eg, cyclopentyl, cyclohexyl). In one embodiment, R can be an alkyl group having at least 7, at least 8, at least 9, or at least 10 carbons in size. In one embodiment, the alkyl group substitution is separated from the fused thiophene ring system by at least two carbons. Examples of substituted alkyl groups according to this embodiment include 6-hydroxyhexyl and 3-phenylbutyl. The choice of R ₁ and R ₂ moieties depends on the end use of the composition containing the fused thiophene moiety. Any functionality of the substituted alkyl group can be protected to survive subsequent reaction steps. Unsubstituted thiophene-based compositions tend to be relatively insoluble; therefore, in one embodiment, R can be an alkyl group having at least 6 carbons in size. For example, an alkyl group for improving solubility has the formula C _k H _{2K + 1} , where k is an integer greater than or equal to 6.

  In one embodiment, the compound having the previous structure 40 can be synthesized from the β-R-substituted thiophene moiety by the bromination / debromination method shown in FIG. The β-R-substituted thiophene ring system 41 is brominated with molecular bromine to produce the tribrominated compound 42, which is selectively lithiated and protonated at the α-position to provide the desired β-R. -Substituted-β'-bromothiophene 40 is produced. The method of FIG. 8 can also be used to produce a β-brominated fused thiophene moiety from a fused thiophene moiety. The monocyclic β-R-substituted-β'-bromothiophene 40 can be used to make a tricyclic bis (R-substituted) fused thiophene moiety according to the reaction scheme shown in FIG. Monocyclic β-R-substituted-β'-bromothiophene 40 can also be used to prepare monosubstituted fused thiophene moieties according to the reaction scheme shown in FIG. For example, monocyclic thiophene 40 is lithiated and reacted with formylpiperidine, the adduct is hydrolyzed to produce aldehyde 43, which is reacted with 2-mercaptoacetate, cyclized, and carboxylate converted to Removal produces β-R-substituted fused thiophene 14.

  The oxidized condensed thiophene compounds and moieties described herein, eg, 44 and 45, can be prepared by oxidation of the prepared condensed thiophene compound, eg, with MCPBA. Oxidation is generally selective at the central ring of a polycyclic fused thiophene ring system; however, it is believed that any sulfur atom in the fused thiophene can be oxidized.

In one embodiment, the compound comprising the moiety 3 ′ or 4 ′ has the formula 210 or 220:

Can be produced by reacting a compound comprising: with a compound having the formula (R ⁵ ) ₃ Sn—Ar—Sn (R ⁵ ) ₃ , where n is an integer greater than or equal to 1; In the embodiment, n is an integer of 2 or more; m is an integer of 1 or more; R ₁ and R ₂ are independently hydrogen or an alkyl group, and at least one of R ₁ and R ₂ Is an alkyl group; Ar comprises an aryl group and R ⁵ is an alkyl group. In this embodiment, the dibromofused thiophene is coupled with a bis-stannylaryl group. The coupling reaction is generally performed in the presence of a catalyst such as Pd (0). FIG. 18 illustrates one embodiment of this method, where dibromo-fused thiophene (formula 210, n = 2, m = 1) is 2,5′- in the presence of Pd (PPh ₃ ) _4. Coupling with distannyltrimethyl-bithiophene to form a copolymer. Using this methodology, it is possible to produce copolymers, such as block copolymers, where the values of m and o at 3 ′ and 4 ′ vary depending on the desired molecular weight of the copolymer. obtain.

  In another embodiment, a series of synthetic steps can produce a compound comprising a moiety 3 "or 4". The fused thiophene core may be synthesized and brominated as described herein. The dibromo-fused thiophene may then be reacted sequentially with butyllithium and trimethyltin chloride to form a bis-tin-substituted fused thiophene as shown in FIG. Formation of the dipyrropyrrole moiety can be carried out by the reaction scheme shown in Tieke et al., Beilstein, J. ORG. CHEM. 830 (2010), which is hereby incorporated by reference in its entirety. -Bis (5-bromothiophen-2-yl) -2,5-diheptadecylpyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione is described in FIG. The fused thiophene moiety and dipyrropyrrole moiety may be combined to form 3 "or 4" by any standard coupling reaction. In some embodiments, the fused thiophene moiety and the dipyrropyrrole moiety may be coupled by a Stille type coupling reaction as shown in FIG. In the reaction of FIG. 22, since the reliability is good, a palladium (II) catalyst is used, but a palladium (O = 0) catalyst such as tetrakistriphenylphosphine palladium (0) may be used.

  In another embodiment, a fused thiophene compound comprising moiety 300 or 301 can be produced by 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 tributyltin compound in a Still type reaction in the presence of a palladium catalyst to produce an aryl-containing polymer. Alternatively, the fused thiophene core is reacted sequentially with butyllithium and trimethyltin chloride to form a bis-tin substituted fused thiophene, which is then reacted with a brominated aryl moiety in a Still-type reaction to conjugate. A polymer may be formed (FIG. 25). In the reaction of FIG. 25, since the reliability is good, a palladium (0) catalyst is used, but a palladium (II) -based catalyst may be used.

Fused thiophene and oxidized condensed thiophene oligomers and polymers can be prepared using methodologies similar to those used to make the oligo- and poly (thiophene) described above. For example, iron (III) compounds (eg, FeCl ₃ , Fe (acac) ₃ ) can be used to oxidatively oligomerize or polymerize α, α′-dihydrofused thiophene moieties, or organomagnesium mediated In the reaction, it can be brominated and coupled. The 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 those skilled in the art. Can do. The fused thiophene moieties and oxidized fused thiophene moieties described herein can be incorporated into other backbone and side chain polymers using techniques known in the art. The fused thiophene compound is believed to be oxidized prior to inclusion in the oligomer or polymer. Alternatively, the fused thiophene compound can be included in the oligomer or polymer and then oxidized.

  The following examples are set forth to provide those skilled in the art with a complete disclosure and description of how to make and evaluate the materials, articles, and methods described and claimed herein. It is intended to be exemplary only and is not intended to limit the scope of the description. Efforts have been made to ensure accuracy with respect to numbers (eg, amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is expressed in ° C or is at ambient temperature, and pressure is at or near atmospheric. Variations in reaction conditions such as component concentration, desired solvent, solvent mixture, temperature, pressure and other reaction ranges and conditions that can be used to optimize the purity and yield of the product resulting from the described process There are many and combinations. Only reasonable and routine experimentation will be required to optimize such process conditions.

Example 1 Di-β-Substituted Thieno [3,2-b] thiophene 3,6-Dihexylthieno [3,2-b] thiophene 57 is synthesized as shown in the reaction scheme of FIG.

2,4,5-Tribromo-3-hexylthiophene (51). 3-Hexylthiophene (50) (100 g, 0.595 mol) was mixed with 200 mL acetic acid. Bromine (88 mL, 1.33 mol) was added dropwise to the mixture. After the addition of bromine, the resulting mixture was stirred at room temperature for 4 hours, heated at 60-70 ° C. overnight, then poured into 800 mL of ice water and neutralized with 6M aqueous NaOH. This mixture was extracted with ethyl acetate (3 × 100 mL). The combined organic layer was washed with brine (2 × 100 mL) and water (100 mL) and dried over MgSO ₄ . Evaporation of the solvent gave the crude product 51 (234 g, 97.1% crude yield). This crude product is sufficiently pure to be used in subsequent reactions. ¹ H NMR (CD ₂ Cl ₂ ): δ 2.64 (t, 2H), 1.51 (m, 2H), 1.32 (m, 6H), 0.89 (t, 3H). ¹³ C NMR: 143.69, 117.86, 111.48, 110.18 , 33.62, 32.86, 30.96, 30.52, 24.70, 16.00.

3-Bromo-4-hexylthiophene (52). Compound 51 (70 g, 0.173 mol) was mixed with dry THF (400 mL). To this mixture, n-butyllithium (138 mL, 2.5 M in hexane, 0.345 mol) was added dropwise at −78 ° C. under an argon atmosphere. The resulting mixture was stirred for 10 minutes and then water (30 mL) was added to quench the reaction. The THF was evaporated and the organic layer was extracted with ethyl acetate (2 × 100 mL). The combined organic layer was washed with brine (2 × 100 mL) and water (70 mL) and dried over MgSO ₄ . After evaporation of the solvent, the resulting crude product was purified by vacuum distillation (72-74 ° C., 0.17 mbar (17 Pa)) to give 52 (35.3 g, 82.6% yield). ¹ H NMR (CD ₂ Cl ₂ ): δ 7.22 (s, 1H), 6.96 (s, 1H), 2.57 (t, 2H), 1.61 (m, 2H), 1.32 (m, 6H), 0.88 (t, 3H). ¹³ C NMR: 141.92, 122.87, 120.95, 112.89, 31.88, 30.07, 29.53, 29.20, 22.88, 14.14.

1- (3-Bromo-4-hexyl-2-thienyl) heptanone (53). To a mixture of compound 52 (24.7 g, 0.1 mol) and AlCl ₃ (26.8 g, 0.2 mol) in dry CH ₂ Cl ₂ (100 mL) was added heptanoyl chloride (14.9 g, 0.1 mol). ) Was added dropwise at room temperature. This mixture was allowed to react for about 2 hours, or GC / MS analysis showed 3: 1 of the desired compound 53 and its regioisomer 1- (4-bromo-3-hexyl-2-thienyl) heptanone (54). Stir until it indicates that a mixture has formed. The reaction mixture was poured into 200 mL 6M HCl and washed with water (3 × 50 mL). The organic layer was then dried over MgSO ₄ . Evaporation of the solvent gave 34.7 g of a crude mixture of compounds 53 and 54, which was used for the next reaction without separation, ie without further purification.

3,6-Dihexylthieno [3,2-b] thiophene-2-carboxylic acid (55). Mixture of compounds 53 and 54 (66.5 g, 0.185 mol) mixed with a catalytic amount of 18-crown-6 and K ₂ CO ₃ (53.6 grams, 0.39 mole) in DMF in 200mL and did. The mixture was heated to 60-70 ° C. and ethyl 2-mercaptoacetate (20.3 mL, 0.185 mol) was added dropwise. The reaction mixture was stirred at 60-70 ° C. overnight and then poured into water (800 mL). The organic component was extracted with ethyl acetate (3 × 100 mL) and the combined organic extracts were washed with brine (2 × 100 mL) and then with water (100 mL). The solvent is removed by evaporation, and the residue is dissolved in tetrahydrofuran (300 mL) to form a solution that contains lithium hydroxide (84 mL, 10% aqueous solution), methanol (50 mL) and a catalytic amount of tetrabutyl iodide. Ammonium was added. The mixture was heated at reflux for 3 hours, after which the solvent was removed by evaporation and the residue was acidified with concentrated HCl (aq) (50 mL). After dilution with 200 mL of water, the organic component was extracted with ethyl acetate (3 × 100 mL). The combined organic layers were washed with brine (2 × 100 mL) then water (100 mL) and dried over MgSO ₄ . After evaporation of the solvent, column chromatography (SiO ₂ /5% ethyl acetate in hexane, 20% ethyl acetate in hexane to completely elute compound 55) is used to remove compound 55 unreacted. Compound 54 was isolated to give pure compound 55 (30 g, 46.1% yield). ¹ H NMR (CD ₂ Cl ₂ ): δ 7.24 (s, 1H), 3.18 (t, 2H), 2.73 (t, 2H), 1.75 (m, 4H), 1.34 (m, 14H), 0.89 (m, ^{6H) 13 C NMR:. 169.15} , 146.25, 143.10, 141.49, 136.14, 126.67, 126.11, 31.99, 29.74 (6C), 22.99, 14.24.

3,6-Dihexylthieno [3,2-b] thiophene (57). A mixture of compound 55 (30 g, 0.085 mol), powdered copper (3.76 g) and quinoline (80 mL) was heated at 264-260 ° C. in a Wood metal bath. When no carbon dioxide gas bubbles were detected (about 2 hours), the mixture was cooled to room temperature and hexane (200 mL) was added. The mixture was washed repeatedly with HCl (aq) (1-2 M) to remove quinoline. The remaining organic layer was dried over MgSO ₄ and concentrated by evaporation to leave a residue that was purified by column chromatography (SiO ₂ / hexane) to give compound 57 (18 g, 68.4%). It was. mp 57.5-59.1 ℃, ¹ H NMR (CD ₂ Cl ₂ ): δ6.97 (s, 2H), 2.70 (t, 4H), 1.73 (m, 4H), 1.37 (m, 12H), 0.88 (t, 6H). ¹³ C NMR: 136.56, 134.96, 109.80, 31.94, 29.31, 29.28, 28.47, 22.96, 14.22.

  The same reaction sequence is used to produce 3,6-didecylthieno [3,2-b] thiophene (58).

Example 2 Mono-β-Substituted Thieno [3,2-b] thiophene 3-Hexylthieno [3,2-b] thiophene 58 is synthesized as shown in the reaction scheme of FIG.

1- (3-Bromothienyl) heptanone (59). To a mixture of 3-bromothiophene (60) (16.3 g, 0.1 mol), AlCl ₃ (26.8 g, 0.2 mol) and CH ₂ Cl ₂ (100 mL) was added heptanoyl chloride (14.9 g, 0 mol). 0.1 mol) was added dropwise at room temperature. The resulting mixture was stirred for about 2 hours or until GC / MS analysis showed complete conversion of compound 60 to compound 59. The reaction mixture was poured into cold HCl (aq) (6M, 200 mL). The organic component was extracted with hexane (3 × 100 mL). The combined organic layer was washed with brine (2 × 100 mL) and water (100 mL). After drying over MgSO ₄ , the desired crude product was purified by column chromatography (SiO ₂ / hexane) to give compound 59 (25.1 g, 91.3% yield). GC / MS: 275 g / mol (M) ¹ H NMR (CD ₂ Cl ₂ ): δ 7.53 (d, 1H), 7.12 (d, 1H), 3.01 (t, 2H), 1.71 (m, 2H), 1.38 (m, 6H), 0.92 (t, 3H).

Ethyl 3-hexylthieno [3,2-b] thiophene-2-carboxylate (61). Compound 59 (35.4 g, 0.13 mol) and K ₂ CO ₃ (27.6g, 0.2 mol) was mixed with N, N- dimethylformamide and (100 mL). A catalytic amount of 18-crown-6 (about 25 mg) was added and ethyl 2-mercaptoacetate (14.0 mL, 0.13 mol) was added dropwise to the mixture at 60 ° C. The mixture was stirred overnight and poured into water (500 mL). The organic component was extracted with ethyl acetate (3 × 80 mL). The combined organic layer was washed with brine (2 × 100 mL) and water (100 mL). The organic layer was then dried over MgSO ₄ . After evaporation of the solvent, crude compound 61 was obtained and purified by column chromatography (SiO ₂ /5% ethyl acetate in hexane) to give pure compound 61 (32.1 g, 84.5%). . GC / MS: 296 g / mol (M). ¹ H NMR (CD ₂ Cl ₂ ): δ 7.56 (d, 1H), 7.24 (d, 1H), 4.34 (q, 2H), 3.15 (t, 2H) , 1.71 (m, 2H), 1.32 (m, 6H), 0.88 (m, 6H) 13 C NMR:. 163.24, 143.31, 141.85, 141.09, 131.13, 128.44, 120.35, 61.25, 31.99, 29.72 ( overlap), 22.98 , 14.52, 14.23.

  3-Hexylthieno [3,2-b] thiophene-2-carboxylic acid (62). Compound 61 (32.1 g, 0.11 mol) was charged in a 500 mL flask with lithium hydroxide (10% in water, 50 mL), THF (100 mL), MeOH (30 mL) and a catalytic amount of tetrabutylammonium iodide (approximately 20 mg). The mixture was heated at reflux overnight, cooled to room temperature and acidified with concentrated HCl. The resulting yellow solid was collected by filtration and washed thoroughly with water. The solid was then heated with hexane (100 mL) and cooled to room temperature. After filtration, the solid was collected and dried in vacuo to give compound 62 (28.0 g, 96.7% yield) as a pale yellow powder. m.p .: 110.7-112.4 ° C.

3-Hexylthieno [3,2-b] thiophene (58). A mixture of compound 62 (14.6 g, 0.054 mol), powdered copper (2.00 g) and quinoline (80 mL) was heated at about 260 ° C. in a Wood metal bath. When no CO ₂ bubbles were detected (about 2 hours), the mixture was cooled to room temperature and hexane (200 mL) was added. The mixture was washed repeatedly with HCl (aq) (1-2 M) to remove quinoline. The organic layer was dried over MgSO ₄ and concentrated by evaporation. The residue was purified by column chromatography (SiO ₂ / hexane) to give Compound 58 (25.1 g, 90.3% yield). GC / MS: 224 g / mol (M). ¹ H NMR (CD ₂ Cl ₂ ): δ 7.36 (m, 1H), 7.25 (m, 1H), 7.01 (m, 1H), 2.73 (t, 2H) , 1.69 (m, 2H), 1.34 (m, 6H), 0.89 (t, 3H). ¹³ C NMR: 140.39, 139.13, 135.39, 127.01, 122.19, 120.26, 32.01, 30.29, 29.43, 23.01, 14.24.

Example 3 Di-β-substituted dithieno [3,2-b: 2 ′, 3′-d] thiophene and di-β-substituted dithieno [3,2-b: 2 ′, 3′-d] thiophene- 4,4-dioxide 3,6-didecylthieno [3,2-b] thiophene 63 and 3,6-didecylthieno [3,2-b] thiophene-4,4-dioxide 64 are shown in the reaction scheme of FIG. Synthesize like

1,1 ′-(3,4-Bromo-2,5-thienyl) diundecanol (65). Butyllithium (160 mL, 0.4 mol, 2.5 M in hexane) was added dropwise at −78 ° C. to a solution of tetrabromothiophene 36 (80.0 g, 0.2 mol) and THF (500 mL). Undecylaldehyde (DecCHO) (69.7 g, 0.41 mol) was added and the reaction mixture was stirred for 2 hours. The THF solvent was then removed by evaporation and the organic residue was extracted with hexane. The combined organic layer was washed with brine (2 × 100 mL) and water (100 mL) and dried over MgSO ₄ . The crude product was purified by column chromatography (SiO ₂ /5% ethyl acetate in hexanes) to yield compound 65 (84.1 grams, 72.5% yield). ¹ H NMR (CD ₂ Cl ₂ ): δ 5.02 (s, br, 2H), 1.79 (m 4H), 1.28 (m, 32H), 0.88 (t, 6H). ¹³ C NMR: 143.25, 109.67, 70.53, 38.31, 31.96, 29.75, 29.70, 29.61, 29.55, 29.21, 25.68, 22.84, 14.09.

1,1 ′-(3,4-Bromo-2,5-thienyl) diundecanone (66). A chromic acid solution was prepared by dissolving sodium dichromate dihydrate (100 g, 0.34 mol) in water (300 mL), then concentrated sulfuric acid (136 g) was added and the resulting solution was Dilute to 500 mL. To compound 65 (80.0 g, 0.137 mol) mixed with acetone (300 mL), a chromic acid solution (260 mL) was added dropwise at room temperature. The mixture was stirred overnight, after which a large amount of solid formed in the reaction mixture. Most of the acetone was gently transferred to another container and the remainder of the mixture was extracted with ethyl acetate (2 × 100 mL). The combined organic layer was washed with brine (3 × 50 mL) and dried over MgSO ₄ . The solvent was evaporated and the residue was mixed with ethanol (100 mL), white pure compound 66 solidified and collected by filtration (72.0 g, 90.5% yield). mp 69.5-70.8 ℃. ¹ H NMR (CD ₂ Cl ₂ ): δ 3.07 (t, 4H), 1.74 (m, 4H), 1.28 (m, 28H), 0.88 (t, 6H). ¹³ C NMR: 192.49 , 141.99, 118.82, 42.03, 32.13, 29.79, 29.71, 29.62, 29.55, 29.29, 24.16, 22.92, 14.11.

Diethyl 3,5-didecyldithieno [3,2-b: 2 ′, 3′-d] thiophene-2,6-dicarboxylate (67). Compound 66 (30.0 g, 0.052 mol) was mixed with potassium carbonate (28.7 g, 0.21 mol) and N, N-dimethylformamide (100 mL). To this mixture, ethyl 2-mercaptoacetate (11.5 mL, 0.104 mol) was added dropwise at 60 ° C. The reaction mixture was stirred at 60 ° C. for 48 hours under a nitrogen atmosphere and then poured into water (500 mL). The organic component was extracted with ethyl acetate (3 × 100 mL). The combined organic layer was washed with brine (2 × 100 mL) and water (50 mL) and dried over MgSO ₄ . The solvent was evaporated and the residue was purified by column chromatography (SiO ₂ /5% ethyl acetate in hexane) to give compound 67 (19.1 g, 59.3% yield) as a sticky solid. . ¹ H NMR (CD ₂ Cl ₂ ): δ 4.36 (q. 4H), 3.15 (t, 4H), 1.73 (m, 4H), 1.39 (m, 36H), 0.87 (m, 6H). ¹³ C NMR: 162.86, 145.47, 144.51, 133.05, 128.99, 61.63, 32.33, 29.99 (overlapping), 23.11, 14.53, 14.31.

3,5-Didecanyldithieno [3,2-b: 2 ′, 3′-d] thiophene-2,6-dicarboxylic acid (68). Compound 67 (10.2 g, 0.017 mol) mixed with lithium hydroxide (1.0 g in 10 mL water), THF (100 mL), MeOH (20 mL) and a catalytic amount of tetrabutylammonium iodide (about 35 mg). did. The mixture was heated at reflux overnight and then most of the solvent was evaporated. The residue was acidified with concentrated HCl (30 mL) and a solid formed which was collected by filtration, washed well with water and dried in vacuo to give compound 68 (8.6 g, 98% yield). It was. mp 280.1 ¹ H NMR (CD ₂ Cl ₂ ): δ 3.24 (t, 4H), 1.72 (m, 2H), 1.29 (m, 30H), 0.88 (t, 6H). ¹³ C NMR: 168.46, 148.24, 146.58 , 136.32, 35.91, 33.64, 28.91 (m, overlap), 26.60, 17.49.

3,5-Didecyldithieno [3,2-b: 2 ′, 3′-d] thiophene (63). Compound 68 (8.6 g, 0.016 mol), powdered copper (0.7 g) and quinoline (50 mL) were mixed and heated at 250-260 ° C. in a Wood metal bath. When no carbon dioxide gas bubbles were detected (about 2 hours), the mixture was cooled to room temperature and hexane (200 mL) was added. The mixture was washed repeatedly with HCl (1-2 M in water) to remove quinoline. The organic layer was dried over MgSO ₄ , concentrated by evaporation and the residue was purified by column chromatography (SiO ₂ / hexanes) to give compound 63 (3.4 g, 47.4%). ¹ H NMR (CD ₂ Cl ₂ ): δ 6.97 (s, 2H), 2.73 (t, 4H), 1.78 (m, 4H), 1.27 (m, 28H), 0.88 (t, 6H). ¹³ C NMR: 141.89, 136.75, 130.99, 120.57, 32.33, 30.02, 29.79, 29.74, 29.15, 23.10, 14.28.

  Compounds 64 and 69 are prepared using the method described in Sogiu et al., 68 J. ORG. CHEM. 1512-1520 (2003), cited herein.

3,5-didecylthieno [3,2-b: 2 ′, 3′-d] thiophene-4,4-dioxide (64). 3-Chloroperbenzoic acid (6.1 g, 0.035 mol) in 20 mL of dichloromethane was added dropwise to a solution of 63 (3.64 g, 8.18 mol) in 20 mL of dichloromethane. The mixture was stirred overnight at room temperature and then washed successively with 10% potassium hydroxide, 10% NaHCO ₃ and brine. The organic layer was dried over MgSO ₄ and the solvent removed by evaporation. The crude product was purified by column chromatography (SiO ₂ /5% ethyl acetate in hexanes) to give compound 64 (1.4 g, 35.9% yield) as a yellow solid. mp 58.7-60.3 ° C. ¹ H NMR (CD ₂ Cl ₂ ) δ 6.94 (s, 2H), 2.73 (t, 4H), 1.72 (m, 4H), 1.27 (m, 28H), 0.88 (t, 6H) ¹³ C NMR: 142.99, 139.06, 136.36, 124.51, 32.27, 30.11, 29.95, 29.91, 29.68, 29.48, 29.51, 28.51, 23.04, 14.22.

Diethyl 3,5-didecyldithieno [3,2-b: 2 ′, 3′-d] thiophene-4,4-dioxide-2,6-dicarboxylate (69). 3-Chloroperbenzoic acid (1.2 g, 6.9 mmol) in 20 mL dichloromethane was added dropwise to a solution of 67 (3.64 g, 8.18 mol) in 20 mL dichloromethane. The mixture was stirred overnight at room temperature and then washed successively with 10% potassium hydroxide, 10% NaHCO ₃ and brine. The organic layer was dried over MgSO ₄ and the solvent removed by evaporation. The crude product was purified by column chromatography (SiO ₂ /5% ethyl acetate in hexanes) to give compound 69 (0.56 g, 53% yield) as a waxy solid. ¹ H NMR (CD ₂ Cl ₂ ) δ 4.39 (q, 4H), 3.13 (t, 4H), 1.72 (m, 4H), 1.27 (m, 34H), 0.88 (t, 6H). ¹³ C NMR: 161.41 , 145.52, 144.77, 137.56, 132.89, 62.03, 32.11, 30.59, 29.82, 29.78, 29.75, 29.53, 29.49, 27.88, 22.89, 14.21, 14.07.

  3,5-dihexyldithieno [3,2-b: 2 ′, 3′-d] thiophene and 3,5-dihexyldithieno [3,2-b: 2 ′, 3′-d] thiophene-4, The reaction scheme of FIG. 12 is also used to produce 4-dioxide.

Example 4 Di-β-substituted thieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene 3,7-didecylthieno [3,2-b] Thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene 70 is synthesized as shown in the reaction scheme of FIG.

2,4-di (1-hydroxydecyl) -3,6-dibromothieno [3,2-b] thiophene (72). According to Fuller et al., 1 J. CHEM. SOC., PERKIN TRANS, 3465 (1997), cited here, 2,3,4,5-tetrabromothieno [3,2-b] thiophene (71) Prepared. To a mixture of compound 71 (40.0 g, 0.088 mol) in 300 mL dry THF, butyllithium (70 mL, 0.175 mol, 2.5 M in hexane) was added dropwise at -78 ° C. The resulting mixture was stirred for an additional 10 to 20 minutes and undecylaldehyde (30.0 g, 0.176 mol) was added dropwise. The mixture was warmed to room temperature and stirred overnight. Water (20 mL) was added and the solvent was removed by evaporation. The residue was mixed with hexane (300 mL) and the resulting solid was collected by filtration. The solid is then dried under vacuum to yield compound 72 (47.0 g, 83.9% yield), which is used without further purification. mp: 116.0-118.0 ¹ H NMR (CD ₂ Cl ₂ ): δ 5.15 (m, 2H), 2.31 (broad, 2H), 1.91 (m, 4H), 1.31 (m, 32H), 0.92 (t, 6H). ¹³ C NMR: 144.06, 109.05, 70.58, 38.77, 32.36, 30.06, 30.04, 29.99, 29.77, 29.65, 26.09, 23.12, 14.29.

  2,4-Undecanyl-3,6-dibromothieno [3,2-b] thiophene (73).

Compound 72 (30.0 g, 0.047 mol) was mixed with acetone (200 mL). To this mixture, a chromic acid solution (130 mL) was added dropwise at room temperature. The mixture was stirred overnight at room temperature to form a solid precipitate. Then most of the acetone was gently transferred to another container and the remainder of the mixture was extracted with ethyl acetate (2 × 100 mL). The combined organic layer was washed with brine (3 × 50 mL) and dried over MgSO ₄ . The solvent was evaporated and the residue was mixed with ethanol (100 mL) to precipitate compound 73, which was collected by filtration (18.4 g, 61.7% yield). mp: 120.3-121.5 ° C. ¹ H NMR (CD ₂ Cl ₂ ): δ 3.09 (t, 4H), 1.78 (m, 4H), 1.28 (m, 28H), 0.88 (t, 6H). ¹³ C NMR: 193.15, 143.62, 143.40, 106.70, 41.74, 32.12, 29.79, 29.72, 29.65, 29.55, 29.35, 24.20, 22.91, 14.11.

Diethyl 3,7-didecylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene-2,6-dicarboxylate (74). Compound 73 was mixed with potassium carbonate (16.6 g, 0.12 mol) and N, N-dimethylformamide (100 mL). To this mixture, ethyl 2-mercaptoacetate (6.6 mL, 0.06 mol) was added dropwise at 60 ° C. The reaction mixture was stirred at 60 ° C. for 48 hours under a nitrogen atmosphere and then poured into water (500 mL). The resulting solid was collected by filtration. The crude product was then boiled with ethanol (200 mL) and cooled to room temperature. Filtration and drying produced Compound 74 (14.2 g, 72.4% yield). mp: 130.5-132.2 ¹ H NMR (CD ₂ Cl ₂ ): δ 4.36 (q. 4H), 3.15 (t, 4H), 1.73 (m, 4H), 1.27 (m, 34H), 0.87 (m, 6H). ¹³ C NMR: 163.09, 144.79, 144.29, 135.29, 134.28, 128.54, 61.83, 32.57, 30.32, 30.26, 30.21, 30.07, 30.02, 29.98, 29.79, 23.33, 14.79, 14.49.

  3,7-didecylthieno [3,2-b] thieno [2 ', 3': 4,5] thieno [2,3-d] thiophene-2,6-dicarboxylic acid (75). Compound 74 (14.0 g, 0.021 mol) was combined with lithium hydroxide (1.24 g in 15 mL water), THF (100 mL), MeOH (20 mL) and a catalytic amount of tetrabutylammonium iodide (ca. 35 mg). Mixed. The mixture was heated at reflux overnight and most of the solvent was evaporated. The residue was acidified with conc. HCl (30 mL). The resulting solid was collected by filtration, washed thoroughly with water and dried in vacuo to yield compound 75 (12.5 g, 97.4% yield). m.m .: 315.6-318.5 ° C.

3,7-didecylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene (70). Compound 75 (13.5 g, 0.021 mol) was mixed with powdered copper (0.9 g) in quinoline (80 mL) and the mixture was heated to 250-260 ° C. in a Wood metal bath. When no bubbles of carbon dioxide gas were detected (about 2 hours), the mixture was cooled to room temperature and hot hexane (400 mL) was added. The mixture was then washed repeatedly with HCl (2N, 4 × 50 mL). Some hexane was removed by evaporation and the resulting solid was collected by filtration and recrystallized from hexane to give compound 70 (7.0 g, 60.6% yield). mp: 111.0-113.3 ¹ H NMR (C ₆ D ₆ ): δ 6.53 (s, 2H), 2.51 (t, 4H), 1.64 (m, 4H), 1.27 (m, 28H), 0.89 (t, 6H). ¹³ C NMR: 141.26, 136.42, 133.17, 132.04, 120.73, 32.31, 30.03, 29.96, 29.90, 29.79, 29.66, 29.04, 23.07, 14.28.

Example 5 Attempt to synthesize β-substituted thieno [2,3-d] thiophene using conventional coupling reaction In an unsuccessful attempt to synthesize β-hexyl substituted thieno [2,3-d] thiophene According to the reaction scheme of FIG. Since the electronic properties of fused ring systems are very different from those of simple monocyclic thiophenes, the coupling reactions used for monocyclic thiophenes do not work.

  3,6-Dibromothieno [3,2-b] thiophene (76, 5.2 g, 0.0175 mol) was dissolved in dry diethyl ether (100 mL) and [1,3-bis (diphenylphosphino) propane] Mixed with di-chloronickel (II) (dppp) (0.47 g, 0.05 eq). To this solution, hexyl magnesium bromide (22.0 mL of a 2.0 M solution in diethyl ether, 0.044 mol) was added dropwise. The resulting mixture was heated at reflux for 24 hours. This reaction was monitored by GC / MS. After 24 hours, the starting material disappeared, but no Grignard addition product was formed.

  3-Bromo-6-hexylthieno [3,2-b] thiophene (77, 6.2 g, 0.021 mol) was dissolved in dry diethyl ether (100 mL) and [1,3-bis (diphenylphosphino) Propane] Di-chloronickel (II) (dppp) (0.51 g, 0.05 equiv). To this solution was added hexyl magnesium bromide (13.3 mL of a 2.0 M solution in diethyl ether, 0.027 mol) dropwise. The resulting mixture was heated at reflux for 24 hours. The reaction was monitored by GC / MS and after 6 hours the starting material had disappeared but no Grignard addition product was formed.

Example 6 Poly (β-substituted fused thiophene)
The condensed thiophene polymer is produced using the general procedure described below. This approach is adapted from Andersson et al., 27 MACROMOLECULES 6506 (1994), cited here.

  Monomeric α, α'-dihydro-β, β'-dialkyl fused thiophene compound (10 mmol) is dissolved in 30 mL of chlorobenzene. A suspension of ferric chloride (10 mmol) in 20 mL of chlorobenzene is added to the monomer solution over 30 minutes. The mixture is stirred at room temperature for several hours (eg, 6 to 24 hours). For fused thiophene compounds having a higher number (eg, 4 or more) of rings in the fused ring system, it may be desirable to heat the reaction mixture at 80-90 ° C. for several hours. The reaction mixture is then precipitated from 500 mL of 95: 5 methanol: water. The precipitate was collected by filtration, dissolved in toluene, boiled with concentrated ammonia (3 × 60 mL), and boiled with ethylenediaminetetraacetic acid (0.05 M in water, 2 × 50 mL). The product polymer was precipitated from methanol (500 mL), filtered and dried in vacuo at 70-80 ° C. The following compounds are produced in the following yields: poly (3,6-dihexylthieno [2,3-d] thiophene) (35% yield); poly (3,6-didecylthieno [2,3- d] thiophene) (yield 90%); poly (3,7-didecylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene) (yield) 80%); and poly (3,5-didecylthieno [3,2-b: 2 ′, 3′-d] thiophene-4,4-dioxide) (43% yield).

Example 7 Synthesis of 2-2, 3-3 and 4-4 Dimers and 5 and 7 Ring Systems Synthesis of 2-2 and 3-3 dimers and 5 and 7 ring systems is shown in FIG. Has been.

3,3′-Dibromo-6,6′-didecanyl-2,2′-bisthienothiophene (82). Butyllithium (2.5 M in hexane, 15.6 mL, 0.039 mol) was added dropwise at 0 ° C. to diisopropylamine (4.0 g, 0.039 mol) in dry THF (30 mL). The resulting mixture was held at 0 ° C. for 15 minutes and then 3-bromo-6-decanylthienothiophene (81) (14.0 g, 0.039 mol) dissolved in THF solution (about 30 mL). Was dripped. The mixture was stirred for 1 hour at 0 ° C., after which copper (II) chloride (6.3 g, 0.047 mol) was added. The dark brown mixture was stirred at room temperature for an additional 12 hours. After evaporating all of the solvent, the residue was boiled with toluene (200 mL) and the solid was filtered. The solution was washed with brine (2 × 50 mL) then water (50 mL), dried over MgSO ₄ and the solid collected after cooling. The target compound (82) was produced as a yellow solid. 9.35 g (67%). mp 90.0-91.0 ℃. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.15 (s, 2H), 2.74 (t, 4H), 1.89-1.27 (m, 32 H), 0.89 (t, 6H). ¹³ CNMR: 140.78, 136.25, 133.02, 131.65, 131.23, 120.47, 31.92, 29.61 (duplication), 29.36 (duplication), 28.73, 22.69, 14.11.

3,6-Didecanyl-dithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (83). 3,3′-Dibromo-6,6′-didecanyl-2,2′-bisthienothiophene (82) (8.6 g, 0.012 mol) was dissolved in THF (100 mL). The solution was cooled to −78 ° C. under an argon atmosphere. To this solution, butyl lithium (9.6 mL, 0.024 mol) was added dropwise and the resulting mixture was stirred at -78 ° C. After about 30 minutes, bis (phenylsulfonyl) sulfide (3.8 g, 0.012 mol) was added and the solution was stirred overnight at room temperature, after which the THF was evaporated. The residue was dissolved in hexane (300 mL) and the organic layer was washed with brine (2 × 100 mL) and water (50 mL). The organic layer was then dried over MgSO ₄ . After evaporation of the solvent, the crude product was produced by column chromatography (hot hexane) to give a yellow solid compound. This material was recrystallized from hexane to yield the product (83). 3.2 g (45.3%) mp 107.7-108.5 ° C. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.024 (s, 2H), 2.76 (t, 4H), 1.79-1.28 (m, 32H), 0.88 ( ^13C NMR: 140.58, 138.96, 135.94, 129.80, 122.86, 105.64, 31.92, 29.77, 29.57, 29.33 (duplication), 28.69, 22.69, 14.11.

  Referring to FIG. 15A, 83 can also be prepared by cyclization of 87 with butyllithium and copper chloride.

3,3′-Dibromo-5,5′-didecanyl-2,2′-bisdithieno [3,2-b: 2 ′, 3′-d] thiophene (85). To diisopropylamine (1.13 g, 0.011 mol) in dry THF (30 mL) was added dropwise butyllithium (2.5 M in hexane, 4.4 mL, 0.011 mol) at 0 ° C. The resulting mixture was held at 0 ° C. for 15 minutes and then 3-bromo-5-decanyl-dithieno [3,2-b: 2 ′, 3′-d] thiophene dissolved in THF (40 mL). (84) (4.61 g, 0.011 mol) was added dropwise. The mixture was stirred at 0 ° C. for 1 hour, after which copper (II) chloride (1.77 g, 0.013 mol) was added. The dark green solution was stirred at room temperature for an additional 12 hours. After evaporating all of the solvent, the residue was boiled with toluene (2 × 100 mL) and the solid was filtered. After all the toluene was evaporated, the residue was boiled with toluene (200 mL) and cooled to room temperature. The crystalline product (85) was collected after cooling. Yield 2.0 g (43.8%). mp 140.2-141.1 ° C. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.11 (s, 2H), 2.78 (t, 4H), 1.75-1.28 (m, 32H), 0.86 (t, 6H).

3,7-Didecanyl-bisdithieno {[3,2-b: 4,5-d] [2 ′, 3′-b: 4 ′, 5′-d]} thiophene (86). 3,3′-Dibromo-5,5′-didecanyl-bisdithienothiophene (85) (3 g, 3.62 mmol) was dissolved in dry tetrahydrofuran (80 mL) and cooled to −78 ° C. To this mixture, butyl lithium (7.23 mmol, 2.9 mL) was added dropwise under an argon atmosphere. The resulting mixture was stirred for 1 hour at −78 ° C., after which bis (phenylsulfonyl) sulfide (1.15 g, 3.62 mmol) was added through a solid addition funnel. The resulting mixture was stirred and allowed to warm slowly to room temperature overnight. After evaporating the THF, the residue was refluxed with water (200 mL) and filtered. The solid was then washed with methanol (2 × 50 mL) and refluxed with toluene (200 mL). The hot toluene solution was filtered to remove undissolved solids. After evaporating the toluene, the solid was dissolved in toluene (70 mL) and cooled to room temperature to produce tan needles (1.68 g, 66.3% yield) of the desired compound. mp 140.2-141.1 ° C. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.11 (s, 2H), 2.78 (t, 4H), 1.79-1.28 (m, 32H), 0.88 (t, 6H).

  Referring to FIG. 15B, 86 can also be prepared by cyclization of 88 with butyllithium and copper chloride.

Example 8-Synthesis of tetraalkyl-substituted thienothiophene dimers The synthesis of tri- and tetra-ring tetraalkyl-substituted thienothiophene dimers is shown in Figures 16 and 17, respectively.

A. Tricyclic dimer 2-Bromo-3-decanyldithieno [3,2-b: 2 ′, 3′-d] thiophene (92). 3-Decanyldithieno [3,2-b: 2 ′, 3′-d] thiophene (91) (9.03 g, 0.027 mol) was dissolved in DMF (100 mL). To this solution, N-bromosuccinimide (NBS) (4.78 g, 0.027 mol) in DMF (50 mL) was added dropwise in the dark under an argon atmosphere. The resulting mixture was stirred at 0 ° C. for about 3 hours or until GC / MS showed a single peak at 415. The solution was poured into water (500 mL) and the organic solution was extracted with hexane (3 × 100 mL). The combined organic solution was washed with brine (2 × 50 mL) and then with water (50 mL). After drying with MgSO ₄ , the hexane was evaporated. The crude product was purified by column chromatography and eluted with hexane to yield the desired compound (10.1 g, 90.2% yield). ¹ HNMR (CD ₂ Cl ₂ ): δ 7.39 (d, 1H), 7.29 (d, 1H), 2.74 (t, 2H), 1.74-1.33 (m, 16H), 0.89 (t, 3H). ¹³ CNMR: 140.89, 140.63, 136.00, 131.55, 129.22, 126.58, 121.04, 108.89, 32.31, 29.94, 29.73 (duplication), 29.35, 28.49, 23.09, 14.27.

3-Decanyl-6-dec-1-ynyldithieno [3,2-b: 2 ′, 3′-d] thiophene (93). 2-Bromo-3-decanyldithieno [3,2-b: 2 ′, 3′-d] thiophene (92) (4.16 g, 0.01 mol) was added to 1-decyne (3. 3) in triethylamine (80 mL). 6 g, 0.026 mol), tetrakis (triphenylphosphine) palladium (0.58 g, 0.5 mmol) and copper (I) iodide (0.19 g, 1.0 mmol). The mixture was bubbled with nitrogen for 5 minutes and then heated to 130 ° C. under an argon atmosphere for 16 hours. Triethylamine was evaporated and hexane (150 mL) was added. The mixture was filtered to remove solid salts and the organic layer was washed with 1M hydrochloric acid (aq) (50 mL) and brine (50 mL), then dried over MgSO ₄ . The solvent was removed in vacuo and the residue was purified by silica gel chromatography eluting with hexanes to yield the desired compound (3.87 g, 93.0% yield). ¹ HNMR (CD ₂ Cl ₂ ): δ 7.36 (d, 1H), 7.30 (d, 1H), 2.82 (t, 2H), 2.49 (t, 2H), 1.63-1.27 (m, 28H), 0.88 (m , 6H).

2,3-Didecanyldithieno [3,2-b: 2 ′, 3′-d] thiophene (94). 3-Decanyl-6-dec-1-ynyldithieno [3,2-b: 2 ′, 3′-d] thiophene (93) (36.0 g, 0.076 mol) was dissolved in ethyl acetate (60 mL). 5% Pt / C (9.0 g) was added. The mixture was stirred for 24 hours under H ₂ atmosphere (90 psi) and then filtered. After removal of ethyl acetate, the residue was purified by silica gel chromatography, eluting with hexane to yield the desired compound (29.0 g, 79.9% yield). ¹ HNMR (CD ₂ Cl ₂ ): δ 7.29 (d, 1H), 7.27 (d, 1H), 2.80 (t, 2H), 2.67 (t, 2H), 1.68-1.27 (m, 32H), 0.88 (m , 6H). ¹³ C NMR. 142.88, 140.75, 139.82, 131.69, 131.37, 126.69, 125.04, 120.94, 32.16, 29.85, 22.93, 14.11.

5,6,5 ′, 6′-tetradecanyl-2,2′-bisdithieno [3,2-b: 2 ′, 3′-d] thiophene (95). 2,3-Didecanyldithieno [3,2-b: 2 ′, 3′-d] thiophene (94) (5.16 g, 0.011 mol) and N, N, N ′, N′-tetramethyl Butyllithium (4.5 mL, 0.011 mol) was added dropwise to a hexane solution of ethylenediamine (TMEDA) (1.25 g, 0.011 mol) at room temperature in a nitrogen atmosphere. The resulting mixture was refluxed for 1 hour, after which copper (II) chloride powder was added to the reaction solution, and then the mixture was stirred overnight. The hexane was then removed under vacuum, the residue was boiled with toluene (80 mL), and the resulting residue was removed by filtration. The organic layer was washed with brine (2 × 30 mL) then with water (30 mL) and dried over MgSO ₄ . After removal of toluene, the yellow solid was boiled with acetone (400 mL) and cooled to room temperature to produce the desired crystalline compound (1.26 g, 24.5% yield). ¹ HNMR (CD ₂ Cl ₂ ): δ 7.43 (s, 2H), 2.89 (t, 4H), 2.73 (t, 4H), 1.76-1.34 (m, 64H), 0.93 (m, 12H). ¹³ CNMR ( C ₆ D ₁₂ ): 143.28, 141.09, 140.94, 138.12, 131.66, 131.41, 127.91, 117.18, 32.74, 32.63, 30.44, 30.39, 30.32, 30.29, 30.13, 29.86, 28.58, 23.41, 14.25.

  Referring to FIG. 16, 96 can also be prepared by cyclization of 95 with butyllithium and bis (phenylsulfonyl) sulfide.

B. Tetracyclic dimer 2-formyl-3-bromo-5-decanyldithieno [3,2-b: 2 ′, 3′-d] thiophene (102). Butyllithium (2.5 M in hexane, 10.9 mL, 0.0273 mol) was added dropwise at 0 ° C. to a flask containing diisopropylamine (2.76 g, 0.027 mol) in dry THF (100 mL). The resulting mixture was held 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) was dissolved in THF (60 mL) and the reaction Dropped into the solution. The mixture was held at 0 ° C. for 1 hour, after which 1-formylpiperidine was added. The resulting mixture was stirred overnight and then the THF was removed. The residue was washed with 10% hydrochloric acid (30 mL) and water (3 × 100 mL). The desired solid compound was purified by crystallization from ethyl alcohol (100 mL) (8.80 g, yield 72.8%). mp 65.5-67.2 ° C.

  2-Carboxylic acid ethyl ester-5-decanyldithieno [2,3-d: 2 ', 3'-d'] thieno [3,2-b: 4,5-b '] dithiophene (103). 2-Formyl-3-bromo-5-decanyldithieno [3,2-b: 2 ′, 3′-d] thiophene (102) (8.80 g, 0.02 mol) was dissolved in DMF (100 mL), Mixed with potassium carbonate (9.66 g, 0.07 mol) and a catalytic amount of 18-crown-6 ether. To this solution, ethyl thioglycolate (2.52 g, 0.021 mol) was added dropwise at 60-70 ° C. The mixture was stirred overnight at this temperature and after completion of the reaction was confirmed by GC / MS, the mixture was poured into water (500 mL). The solid formed from this aqueous solution was removed by filtration. The solid was then washed with water (2 × 200 mL) and methanol (200 mL). GC / MS showed a single peak at 465. After drying under vacuum, the desired compound is used without further purification (8.0 g, 86% yield). m.p. 59.4-62.0 ° C.

  2-Carboxylic acid-5-decanyldithieno [2,3-d: 2 ', 3'-d'] thieno [3,2-b: 4,5-b '] dithiophene (104). 2-Carboxylic acid ethyl ester-5-decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (103) (9.3 g, 0.02 mol) was dissolved in THF (100 mL). To this solution, methanol (20 mL) and lithium hydroxide (10% solution, 7 mL) were added along with a sufficient amount of tetrabutylammonium iodide as a catalyst. The mixture was refluxed overnight, then about 2/3 of the solvent was removed and the residue was poured into concentrated HCl (100 mL). The solid was collected by filtration and washed with water until neutral. After drying, 6.06 g of the desired compound was obtained (yield 69.3%). m.p. 225-227 ° C.

5-Decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (105). 2-Carboxylic acid-5-decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (104) (6.06 g, 0. 014 mol) was dissolved in quinoline (80 mL) and then powdered copper (0.62 g, 9.7 mol) was also added to the mixture. The mixture was heated to 240-260 ° C. and maintained at this temperature until no bubbles were observed (about 1 hour). The mixture was cooled to room temperature and poured into 30% HCl (aq) (300 mL). The organic solution was extracted with hexane (150 mL) and washed several times with 10% HCl (aq) to remove quinoline from the organic layer. The organic layer was then dried over MgSO ₄ . After removal of the solvent, the residue was recrystallized from ethanol to yield 4.44 g of the desired compound (81.3% yield). mp: 88.3-89.6 ° C. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.38 (d, 1H), 7.32 (d, 1H), 6.99 (m, 1H), 2.73 (t, 2H), 1.77 (m, 2H ), 1.35-1.27 (m, 14H) , 0.87 (t, 3H) 13 CNMR:. 141.29, 140.59, 136.72, 133.51, 132.32, 132.27, 131.51, 126.29, 121.15, 121.02, 32.32, 30.00, 29.96, 29.78 ( overlapping ), 29.73, 29.11, 23.09, 14.28.

2-Bromo-3-decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (106). 5-Decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (105) (5.56 g, in dry DMF (50 mL)) 0.0113 mol) NBS (2.01 g, 0.0113 mol) in DMF (30 mL) was added dropwise at 0 ° C. in the dark. The resulting mixture was stirred for 2 hours and poured into water (500 mL). The solid was filtered, washed several times with water, and the product was recrystallized using ethanol (200 mL) to give 5.06 g (94.9% yield). ¹ HNMR (CD ₂ Cl ₂ ): δ 7.43 (d, 1H), 7.34 (d, 1H), 2.77 (t, 2H), 1.74 (m, 2H), 1.36-1.27 (m, 16H), 0.87 (t ^13C NMR: 140.87, 139.54, 135.98, 133.31, 132.11, 131.70, 130.26, 126.77, 121.23, 109.03, 32.32, 29.99, 29.92, 29.75. 29.66, 29.36, 28.50, 23.09, 14.28.

2-dec-1-ynyl-3-decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (107). 2-Bromo-3-decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (106) (2.16 g, 4.6 Mmol) was added to 1-decyne (1.27 g, 9.2 mmol), tetrakis (triphenylphosphine) palladium (0.27 g, 0.23 mmol) and copper (I) iodide (0) in triethylamine (50 mL). 0.087 g, 0.46 mmol). The mixture was bubbled with nitrogen for 5 minutes and then heated to 130 ° C. under an argon atmosphere for 16 hours. Trimethylamine was evaporated and hexane (150 mL) was added. The mixture was filtered to remove solid salts. The organic layer was washed with 1M hydrochloric acid (aq) (50 mL) and brine (50 mL) and then dried over MgSO ₄ . The solvent was removed under vacuum and the residue was purified by chromatography on silica gel, eluting with hexane to yield the desired compound (2.3 g, 90.2% yield). ¹ HNMR (CD ₂ Cl ₂ ): δ 7.41 (d, 1H), 7.33 (d, 1H), 2.84 (t, 2H), 2.23 (t, 2H), 1.73-1.27 (m, 28H), 0.89 (m , 6H).

2,3-Didecanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (108). 2-dec-1-ynyl-3-decanyldithieno [2,3-d: 2 ′, 3′-d ′] thieno [3,2-b: 4,5-b ′] dithiophene (107) (2.2 g 4.15 mmol) was dissolved in ethyl acetate (30 mL) and to this solution was added 5% Pt / C (0.5 g). The mixture was stirred for 24 hours under H ₂ atmosphere (90 psi) and then filtered. After removal of ethyl acetate, the residue was purified by silica gel chromatography eluting with hexane to yield the desired compound (2.0 g, 90.5% yield). mp 50.9-52.5 ° C. ¹ HNMR (CD ₂ Cl ₂ ): δ 7.41 (d, 1H), 7.33 (d, 1H), 2.83 (t, 2H), 2.50 (t, 2H), 1.73-1.26 (m, 32H), 0.87 (m, 6H ) 13 CNMR:. 140.85,140.40,139.93, 133.38, 133.14, 132.22, 129.69, 121.17, 120.09, 98.92, 32.29, 32.25, 29.99, 29.94, 29.72, 29.63, 29.52, 29.33, 29.18 , 29.06, 28.94, 23.05, 14.23.

  Referring to FIG. 17, 109 can be prepared by coupling 108 with butyl lithium and copper chloride. Cyclization of 109 to produce 110 can be accomplished by reacting 109 with butyllithium and bis (phenylsulfonyl) sulfide.

Example 9-Synthesis of polymer containing fused thiophene moiety Poly-3,6-dihexyl-thieno [3,2-b] thiophene (PDC6FT2). The monomer 3,6-dihexyl-thieno [3,2-b] thiophene (3.08 g, 0.01 mol) is dissolved in chlorobenzene. A suspension of FeCl ₃ in chlorobenzene is added to the monomer solution within 30 minutes. The final concentrations of monomer and FeCl ₃ are 0.05M and 0.2M, respectively. The mixture is stirred at room temperature for 6-24 hours. When this polymer solution is poured into a 5% aqueous methanol solution, a precipitate is formed. The polymer is collected by filtration and redissolved in toluene. The toluene solution is then boiled with concentrated ammonia (3 × 60 mL) and then boiled twice with ethylenediaminetetraacetic acid (EDTA) (0.05 M in water) (2 × 50 mL). The resulting toluene is slowly added dropwise to methanol (500 mL) to precipitate the polymer. After filtration, the polymer is dried overnight in a vacuum oven (70-80 ° C.) to produce the product PDC6FT2 in 35% yield. Using this method, poly-3,6-didecanyl-thieno [3,2-b] thiophene (PDC10FT2) can also be produced in 90% yield.

The methods described above may also be used to produce the polymers PDC10FT4 (80% yield) and PDC10FTS3 (43% yield).

Example 10-Synthesis of bithiophene and fused thiophene copolymer 2,3-Dibromo-3,5-didecanyldithieno [3,2-b; 2 ', 3'-d] thiophene (1.0 g, 1.57 mmol) ), 2,5′-distannyltrimethyl-bithiophene (0.772 g, 1.57 mmol) and tetrakis (triphenylphosphine) palladium (0) (0.095 g, 0.082 mmol) in chlorobenzene under an argon atmosphere. Dissolve in (30 mL). The resulting mixture is heated to 150 ° C. under an argon atmosphere for 14 hours and then precipitated into methanol (400 mL). The collected solid polymer is washed with acetone (100 mL) and washed with acetone in a Soxhlet extractor. The solid polymer is then dissolved in chlorobenzene (100 mL) and filtered through a glass filter. After evaporating most of the chlorobenzene, the polymer shown below is precipitated again from methanol (300 mL). The red polymer powder is dried under vacuum to produce 0.9 grams (90.1% yield).

2,7-dibromo-3,6-didecanylpentathienoacene (0.89 g, 1.19 mmol), 2,5′-distannyltrimethyl-bithiophene (0.59 g, 1.57 mmol) and tetrakis (Triphenylphosphine) palladium (0) (0.072 g, 0.062 mmol) is reacted as described above. The polymer is washed with hexane in a Soxhlet extractor. The final polymer shown below is dried under vacuum to produce 0.8 grams (89% yield).

2,8-dibromo-3,7-didecanylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene (1.0 g, 1.45 mmol), 1,4-ditrimethylstannylbenzene (0.59 g, 1.45 mmol) and tetrakis (triphenylphosphine) palladium (0) (0.084 g, 0.073 mmol) are reacted as described above. The polymer, shown below, is dried under vacuum to produce 0.82 grams (93.2% yield).

Example 11-Synthesis of a fused thiophene-diketopyrrolopyrrole moiety and polymer There are several advantages to including a fused thiophene moiety in a polymer further comprising a diketopyrrolopyrrole ("DPP") moiety: 1) The absence of β-hydrogen in the fused thiophene moiety will make the DPP conjugated copolymer structure more stable; 2) Improve copolymer solubility by the possibility of placing large alkyl-based R groups in the fused thiophene moiety 3) The condensed thiophene system consists of large conjugated units, which will improve the electronic and optical properties of the DPP system.

Synthesis of fused thiophene-2,6-dibromo-3,7-diheptadecylthieno [3,2-b] thieno [2 ', 3': 4,5] thieno [2,3-d] thiophene Can be synthesized as described in. 2,6-di (trimethylstannyl) -3,7-diheptadecylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-] in hexane (500 mL) d] A mixture of thiophene (16.0 g, 18.0 mmol) was cooled to 0 ° C. and n-butyllithium (36 mL, 72 mmol) (2M in hexane) was added dropwise with stirring. After complete addition, the mixture was allowed to warm to room temperature and then heated at reflux for 4 hours. The resulting solution was cooled to 0 ° C. and then trimethyltin chloride (90 mL, 90 mmol) (1 M in THF) was added dropwise. After complete addition, the mixture was allowed to warm to room temperature and stirred for an additional 2 hours. While stirring vigorously, ice water (100 g) was added to stop the reaction. Hexane and THF were removed under reduced pressure and the residue was suspended in water (500 mL) and stirred for 1 hour. The suspension was filtered and the solid was resuspended in methanol (500 mL) and stirred for an additional hour. The suspension was filtered and the solid was resuspended in ethanol (500 mL) and finally stirred for 1 hour. The suspension was filtered and the product was recrystallized from a mixture of ethyl acetate (25%) and acetone (75%) (300 mL) as a white solid, as shown in FIG. Thiophene which is 2,6-di (trimethylstannyl) -3,7-diheptadecylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene ("P2TDC17FT4") was produced (17.6 g, 93% yield). mp 78-79 ° C; δ _H (CD ₂ Cl ₂ , 300 MHz) 0.44 (18H, s), 0.88 (6H, t, J = 7.5), 1.18-1.47 (56H, m), 1.67-1.80 (4H, m), 2.75 (4H, t, J = 7.5); δ _C (CD ₂ Cl ₂ , 75 MHz) -7.67 (6C), 14.28 (2C), 23.11 (2C), 29.77 (2C), 29.88 (2C) , 29.94 (2C), 30.10 (20C), 30.51 (2C), 32.35 (2C), 132.60 (2C), 134.78 (2C), 137.01 (2C), 142.98 (2C), 143.22 (2C); m / z ( APCI ⁺ ) 1054.04 [M + H] ⁺ ; Anal. Calc. For C ₅₀ H ₈₈ S ₄ Sn ₂ calculated elemental analysis: C, 56.93; H, 8.41. Found: C, 57.18; H, 8.17.

  Synthesis of the dipyrropyrrole moiety-The formation of the dipyrropyrrole moiety can be carried out by the reaction scheme shown in Tieke et al., Beilstein, J. ORG. CHEM. 830 (2010), cited herein, This is illustrated in FIG. The synthesis of bromothienyl-DPP is based on literature techniques. See, for example, Tamayo et al., 112 J. PHYS. CHEM. 15543-52 (2008) and Huo et al., 42 MACROMOLECULES 6564-71 (2009), both all cited.

  FIG. 21 shows a specific bromothienyl-DPP synthesis. Thiophene-carbonitrile and diisopropyl succinate are combined to form a thiophene-substituted DPP. This reaction is carried out in tert-amyl alcohol and the yield is 82%. This base thienyl DPP is N-alkylated using linear alkyl bromide) followed by alpha bromination of the thiophene group to make it suitable as a Still Coupling comonomer. The final material (bromothienyl-DC17DPP) is purified by recrystallization from chloroform. When bromothienyl-DC16DPP is used, the yield is about 65% in 3 steps.

In a specific exemplary embodiment, a nitrogen-protected, oven-dried, three-necked round bottom flask equipped with a mechanical stirrer, thermometer and reflux condenser was charged with potassium tert-butoxide (67.4 g,. 60 mol) and tert-amyl alcohol (400 mL) were added. The mixture was heated to 105 ° C. for 1.5 hours, 2-thiophenenitrile (55.2 g, 0.50 mol) was added to the mixture and stirring was continued at 105 ° C. for 30 minutes. A mixture of diisopropyl succinate (40.4 g, 0.20 mol) in tert-amyl alcohol (60 mL) was added dropwise over a period of 3 hours with vigorous stirring. The mixture was then stirred at 105 ° C. for an additional 2 hours and then cooled to 50 ° C. at which point a mixture of methanol (300 mL) and water (80 mL) was added. The reaction mixture was heated at reflux for 45 minutes and then cooled to room temperature. The mixture was poured onto 500 g of ice, then concentrated hydrochloric acid (35% aqueous solution) (150 mL) and methanol (750 mL) were added and the mixture was stirred for 45 minutes. The mixture was filtered and the solid was washed with methanol (200 mL). The solid was then suspended in water (1 L) and stirred for 30 minutes before being filtered again. This suspension in water, stirring and filtration was repeated three more times. After the last filtration, the solid was oven dried at 80 ° C. for 16 hours and then dried under vacuum to give the product as a red solid, 3,6-bis (thiophen-2-yl) -2H, 5H -Pyrrolo [3,4-c] pyrrole-1,4-dione (49.7 g, 82% yield) was produced. This compound is used without further purification. mp> 400 ° C. δ _H (d ₆ -DMSO, 300 MHz) 7.30 (2H, dd, J ₁ = 6.0, J ₂ = 3.0), 7.95 (2H, d, J = 6.0), 8.22 (2H, d, J = 3.0), 11.21 (2H, s); δ _C (d ₆ -DMSO, 75 MHz) 108.53 (2C), 128.65 (2C), 130.76 (2C), 131.23 (2C), 132.58 (2C), 136.11 ( 2C), 161.58 (2C); m / z (APCI ⁺ ) 301.20 [M + H] ⁺ .

Next, 3,6-bis (thiophen-2-yl) -2H, 5H-pyrrolo [3,4-c] pyrrole-1,4-dione (19.5 g, 64.9 mmol) and anhydrous potassium carbonate ( 36.8 g, 266 mmol) was stirred in anhydrous N, N-dimethylformamide (DMF) (300 mL) at 130 ° C. under a nitrogen atmosphere for 1 hour. 1-Bromohexadecane (59.5 g, 195 mmol) was then added dropwise and the reaction mixture was stirred at 130 ° C. for an additional 20 hours. The reaction mixture was allowed to cool to room temperature and then poured into ice water (1 L) and the resulting suspension was stirred for 1 hour. The mixture was filtered and the solid was resuspended in water (200 mL) and stirred vigorously for 30 minutes before being filtered again. This suspension in water, stirring and filtration was repeated two more times, then the process was repeated three times, replacing the water with methanol (200 mL). After the last filtration, the solid was dried under vacuum to give the product 2,5-dihexadecyl-3,6-bis (thiophen-2-yl) pyrrolo [3,4-c] pyrrole as a dark red solid -1,4-dione (43.0 g, 88%) was produced. mp 124-125 ° C; δ _H (CD ₂ Cl ₂ , 300 MHz) 0.80 (6H, t, J = 6.0Hz), 1.03-1.38 (52H, m), 1.56-1.72 (4H, m), 3.96 ( 4H, t, J = 9.0) 7.22 (2H, dd, J ₁ = 6.0, J ₂ = 3.0), 7.60 (2H, d, J = 6.0), 8.81 (2H, d, J = 3.0); δ _C ( (CD ₂ Cl ₂ , 75 MHz) 14.69 (2C), 23.18 (2C), 27.31 (2C), 29.71 (2C), 29.82 (2C), 30.00 (4C), 30.16 (12C), 30.37 (2C), 32.37 ( 2C), 42.68 (2C), 120.75 (2C), 129.09 (2C), 130.11 (2C), 131.49 (2C), 135.66 (2C), 140.42 (2C), 161.65 (2C); m / z (APCI ⁺ ) 749.73 [M + H] ⁺ ; Elemental analysis calculated for C ₄₆ H ₇₂ N ₂ O ₂ S ₂ : C, 73.74; H, 9.69; N, 3.74. Found: C, 73.75; H, 9.80; N, 3.72 .

Next, 2,5-diheptadecyl-3,6-bis (thiophen-2-yl) pyrrolo in chloroform (200 mL) preheated to 60 ° C. in a 1 L flask wrapped with aluminum foil for light shielding. To a solution of 3,4-c] pyrrole-1,4-dione (13.0 g) was added N-bromosuccinimide (6.33 g, 35.6 mmol). The reaction was monitored by TLC and stopped as soon as monobrominated species were no longer observed (after about 30 minutes) by pouring into methanol (600 mL) and stirring in an ice bath. The mixture was filtered and the solid was washed with methanol (2 × 200 mL) and then dried under vacuum. The crude product was recrystallized from chloroform (200 mL) to give the product 3,6-bis (5-bromothiophen-2-yl) -2,5-diheptadecylpyrrolo [3 as a dark red solid. , 4-c] pyrrole-1,4-dione (14.2 g, 90%). mp 166-167 ° C; δ _H (CDCl ₂ CDCl ₂ , 300 MHz) 0.80 (6H, t, J = 6.0), 1.10-1.36 (52H, m), 1.56-1.72 (4H, m), 3.87 (4H , t, J = 9.0), 7.17 (2H, d, J = 6.0), 8.53 (2H, d, J = 6.0); m / z (APCI ⁺ ) 907.33 [M + H] ⁺ ; C ₄₆ H ₇₀ Br Elemental analysis calculated for ₂ N ₂ O ₂ S ₂ : C, 60.91; H, 7.78; N, 3.09. Found: C, 60.63; H, 7.68; N, 3.04.

  Synthesis of DPP-FT—The fused thiophene moiety and the diketopyrrolopyrrole moiety may be coupled by any standard coupling reaction, such as a Still coupling reaction. See He et al. 21 ADV. MATER. 2007-2022 (2009), all cited here. As shown in FIG. 22, 3,6-bis (5-bromothiophen-2-yl) -2,5-diheptadecyl in the presence of the catalyst bis (triphenylphosphine) palladium (II) dichloride. Pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione is converted to 2,6-bis (trimethylstannyl) -3,7-diheptadecyl thieno [N, N-dimethylformamide]. 3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene and mixed with poly [(3,7-diheptadecylthieno [3,2-b]. Thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophen-2,6-diyl) [2,5-diheptadecyl-3,6-di (thiophen-2-yl) pyrrolo [3 , 4-c] pyrrole-1,4 (2H, 5H) -dione] -5,5 ′ To form a diyl] ( "PTDC17DPPTDC17FT4"). This reaction may be performed in a nitrogen atmosphere. In the reaction shown in FIG. 22, a palladium (II) catalyst is used to show good reliability, but a palladium (O = 0) catalyst such as tetrakistriphenylphosphine palladium (0) is also used. It's okay.

As another example, a 35 mL microwave reaction vessel equipped with a magnetic stir bar was charged with 2,6-di (trimethylstannyl) -3,7-diheptadecylthieno [3,2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene (1 g), 3,6-bis (5-bromothiophen-2-yl) -2,5-diheptadecylpyrrolo [3,4-c Pyrrole-1,4-dione (0.860 g, 0.948 mmol), tris (dibenzylideneacetone) dipalladium (0) (17.3 mg, 18.9 μmol) and o-tolylphosphine (23.0 mg, 75.6 μmol) was added. The reaction vessel and lid were placed in a nitrogen glove box, where toluene (20 mL) was added, and the lid was fixed to the vessel. The vessel was then removed from the glove box and the reaction was microwaved at 160 ° C. for 2 hours. The mixture was cooled to 50 ° C., removed from the microwave reactor, and then poured into a stirred mixture of methanol and acetylacetone (200 mL + 200 mL). Hydrochloric acid (2 mL, 35% aqueous solution) was added and the mixture was stirred for 16 hours. The mixture was filtered and the polymer was placed in a glass tube equipped with a glass frit soxhlet cylindrical filter paper. The polymer was filtered in a Soxhlet apparatus with acetone (250 mL) for 24 hours and then with hexane (250 mL) for 24 hours. The polymer was then filtered in chloroform (250 mL) in a Soxhlet apparatus. The chloroform solution was poured into methanol (400 mL) with vigorous stirring and then gently stirred for 20 minutes. The polymer is then filtered from the mixture and dried under vacuum to give the product poly [(3,7-diheptadecylthieno [3,2-b] thieno [2 ′, 3 ′] as a purple solid: 4,5] thieno [2,3-d] thiophen-2,6-diyl) [2,5-diheptadecyl-3,6-di (thiophen-2-yl) pyrrolo [3,4-c] pyrrole-1 , 4-dione] -5,5′-diyl] (1.36 g, 97%). Elemental analysis calculated for the repeating unit C ₉₀ H ₁₄₀ N ₂ O ₂ S ₆ : C, 73.31; H, 9.57; N, 1.90. Found: C, 73.16; H, 9.72; N, 1.95.

  Condensed thiophene-based polymers such as P2TDC17FT4 have upper mobility (holes) for charge transport. This theoretical (and practical) limitation will be raised by changing the structure of the polymer and replacing the bithiophene moiety with a mobility-enhancing functionalized DPP moiety. The polymer properties of PTDC16DPPTDC17FT4 are determined using standard test methods. TGA measurements on the material indicate that it is thermally stable up to 400 ° C. (FIG. 23). This TGA shows that the combination of the DPP portion with the FT portion unexpectedly provides a very stable copolymer compared to DPP alone.

The color of the new PTDC16DPPTDC17FT4 polymer is a very dark green, almost black, showing a broad absorption over the visible region of the solar spectrum. UV-visible spectroscopy of both a chloroform solution and a thin film solid state spin-coated from chloroform shows a broad absorption from approximately 550 nm to 950 nm and a less intense absorption from approximately 300 nm to 500 nm (FIG. 24). ). This covers a very wide band in the visible region and gives the polymer a dark green appearance almost close to black. One advantage of this material is its use in photovoltaic devices where such broad solar absorption is desirable. Moreover, such spreading into the IR is highly desirable and is a unique property when combined with low absorption at 300 nm in the same molecule. This makes this polymer more useful as a light absorber in organic photovoltaic devices. This is because light capture efficiency is a major factor in the light efficiency of photovoltaic systems. This strong optical interaction makes this material a good candidate for other optical and / or optoelectronic applications. Furthermore, using a bottom gate top contact device fabricated on a silicon wafer substrate as the gate ground with a 300 nm thermal oxide dielectric layer and gold source and drain electrodes, the compound of structure PTDC16DPPTDC17FT4 is 2 cm ² / It shows a hole mobility of more than V · s, an on / off ratio of more than 10 ⁶ , and a threshold voltage of less than 2V.

Example 12-A condensed thiophene structure attached to an aryl poly [(3,7-diheptadecylthieno [3,2-b] thieno [2 ', 3': 4,5] thieno [2,3-d] thiophene -2,6-diyl) (2,1,3-benzothiadiazole-4,7-diyl)] ("P2BTDC17FT4") (Figure 25)-2,6-dibromo-3,7-diheptadecylthieno [3 , 2-b] thieno [2 ′, 3 ′: 4,5] thieno [2,3-d] thiophene (1.00 g, 0.94 mmol) and 4,7-dibromobenzo [c] -1,2 , 5-thiadiazole (0.28 g, 0.94 mmol) was transferred to a three-necked flask equipped with a stir bar. Nitrogen was bubbled through the flask for several minutes. After sealing the flask, it was placed in a glove box. To this flask was added 0.055 g Pd (PPh ₃ ) ₄ and 30 mL anhydrous chlorobenzene. The flask was heated at about 130 ° C. under a nitrogen atmosphere for 16 hours and then poured into a solution of methanol (200 mL) and concentrated hydrochloric acid (5 mL). The mixture is stirred overnight at room temperature,
The precipitate was then filtered and filtered in a Soxhlet apparatus first with acetone overnight and then with hexane overnight. The collected polymer was dried under vacuum to produce 0.78 grams of blue polymer and poly [(3,7-diheptadecylthieno [3,2-b] thieno [2 ′, 3 ′: 4, 5] thieno [2,3-d] thiophene-2,6-diyl) (2,1,3-benzothiadiazole-4,7-diyl)]. (Lambda _max = 578 nm in the lambda _max = 511 nm, thin film in CHCl ₃ solution).

  It will be apparent to those skilled in the art that various modifications and variations can be made in this description without departing from the spirit and scope of the invention. This description is therefore intended to cover modifications and variations of the embodiments provided herein, provided that they are included in the scope of the appended claims and their equivalents. .

Claims (15)

Formula 3 "or 4":
Wherein m is an integer greater than 0; n is 1 or greater;
X and Y are independently a covalent bond or aryl;
R ₁ and R ₂ 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 R ₄ 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;
A. A compound wherein A and B are independently either S or O.   2. A compound according to claim 1 comprising a polymer.   The compound according to claim 1 or 2, wherein A and B are O.   The compound according to claim 1 or 2, wherein A and B are S. The compound according to any one of claims 1 to 4, wherein at least one of R ₁ and R ₂ contains substituted or unsubstituted alkyl. 6. A compound according to claim 5, wherein at least _one of R < ₁ > and R < ₂ > comprises unsubstituted alkyl. The compound according to any one of claims 1 to 6, wherein at least one of R ₃ and R ₄ contains a substituted or unsubstituted alkyl. At least one of R ₃ and R ₄ comprises an alkyl substituted or unsubstituted with at least 6 carbon atoms, claim 7 compound according.   The compound according to any one of claims 1 to 8, which is contained in a conjugated condensed thiophene polymer or oligomer in which m> 1.   10. A compound according to any one of claims 1 to 9, wherein n is 1 to 15.   11. A polymer comprising a compound according to any one of claims 1 to 10, wherein the polymer has a molecular weight of about 4000 to about 180,000 Da. A process for producing the compound of claim 1,
(I) Structure 1 or 2:
A fused thiophene moiety of
R ₁ and R ₂ 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;
Providing a fused thiophene moiety, wherein X and Y are independently Sn (Alk) ₃ , wherein Alk is a substituted or unsubstituted alkyl;
(Ii) Structure 3:
A dipyrropyrrole portion of
Providing a dipyrropyrrole moiety, wherein X and Y are aryl groups including halide; and (iii) catalyzing the condensed thiophene moiety of structure 1 or 2 to the dipiropyrrole moiety of structure 3 Coupling with
A method comprising:   The method of claim 12, wherein the catalytic reaction is a metal catalyzed reaction.   The method of claim 13, wherein the metal catalyzed reaction is a Stille type coupling.   14. The method of claim 13, further comprising polymerizing the compound of formula 3 "or 4".