Fused thiophene-arylthiadiazole polymers, methods of making such polymers, and uses thereof

Described herein are compositions including heterocyclic organic compounds. More specifically, described herein are bicyclic thiadiazole-based compounds that are combined with fused thiophenes structures, along with methods for making such compounds, and uses thereof.

FIELD

Described herein are compositions including heterocyclic organic compounds. More specifically, described herein are bicyclic thiadiazole-based compounds that are combined with fused thiophenes structures, along with methods for making such compounds, and uses thereof.

TECHNICAL BACKGROUND

Highly conjugated organic materials are currently the focus of a significant amount of research activity in the electronics industry. These compounds are being investigated for use in a variety of applications, including organic field effect transistors (OFETs), organic thin-film transistors (OTFTs), organic light-emitting diodes (OLEDs), electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, and as non-linear optical (NLO) materials. Highly conjugated organic materials may find utility in devices such as RFID tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices.

Conjugated organic materials are of particular interest due to their unique and potentially advantageous electronic and optoelectronic properties. However, in order for a material to be a viable candidate, the devices made from the material need to meet a number of critical parameters. For example, the performance of an OFET device is usually evaluated by several parameters: charge carrier mobility, current On/Off ratio, threshold voltage and the magnitude of the On and Off current. Further, it is advantageous if it is possible to achieve these parameters via a solution deposition process with a minimum number of processing steps. Therefore, semiconducting materials that are stable as inks or in solution form are particularly advantageous.

Materials such as pentacene, poly(thiophene), poly(thiophene-co-vinylene), poly(p-phenylene-co-vinylene) and oligo(3-hexylthiophene) have been intensively studied for use in various electronic and optoelectronic applications. Fused thiophene-containing compounds have also been found to have advantageous properties. For example, bisdithieno[3,2-b:2′,3′-d]thiophene has been found to efficiently π-stack in the solid state, possesses good mobility (up to 0.05 cm2/V·s), and has a high on/off ratio (up to 108). Oligomers and polymers of fused thiophenes, such as oligo- or poly(thieno[3,2-b]thiophene) and oligo- or poly(dithieno[3,2-b:2′-3′-d]thiophene) have also been suggested for use in electronic and optoelectronic devices, and have been shown to have acceptable conductivities and non-linear optical properties. However, there remains a need for organic materials having improved solubility, processability, and oxidative stability.

SUMMARY

Described herein are polymer compositions including heterocyclic organic compounds, such as fused thiophene compounds, methods for making them, and uses thereof. The compositions and methods described herein possess a number of advantages over prior art compositions and methods. For example, the substituted fused thiophene compositions described herein may be made to be more soluble and processable than the analogous unsubstituted thiophene compositions. Polymers and oligomers including the fused thiophene moieties described herein may be processable using conventional spin-coating operations. Further, the compositions described herein may be made with substantially no β-H content, greatly improving the oxidative stability of the compositions.

In an aspect (1), the disclosure provides a polymer comprising the repeat unit of formula 5, 6, 7, or 8:

wherein each R1is independently, an optionally substituted, branched or unbranched alkyl or interrupted alkyl group, a halogen, an optionally substituted aryl or heteroaryl group, or an optionally substituted conjugated group; each R5, R5′, R6, R6′ is independently, hydrogen, an optionally substituted, branched or unbranched alkyl or interrupted alkyl group, a halogen, an optionally substituted aryl or heteroaryl group, or an optionally substituted conjugated group; A and B are N or C—R7, where each R7is independently, hydrogen, halogen, or an optionally substituted, branched or unbranched alkyl or interrupted alkyl group; each Z is independently, NH, S, or O; n is an integer from 1-3; and m is an integer of 1 or more. In an aspect (2), the disclosure provides the polymer of aspect (1), wherein the compound comprises 5 or 6. In an aspect (3), the disclosure provides the polymer of aspect (1), wherein the compound comprises 7 or 8. In an aspect (4), the disclosure provides the polymer of any of aspects (1)-(3), wherein each R1is:

wherein each R10is independently, hydrogen, an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, or a halide, an acyl halide, an acrylate, or a vinyl ether; and r, p, and q are integers of 2 or more. In an aspect (5), the disclosure provides the polymer of aspect (4), wherein each R10is hydrogen; p is an integer of 3 or more; and r and q are integers of 4 or more. In an aspect (6), the disclosure provides the polymer of aspect (5), wherein p is an integer of 6-8 and r and q are integers from 7-15. In an aspect (7), the disclosure provides the polymer of any of aspects (1)-(6), wherein at least one of R5, R5′, R6, or R6′is an optionally substituted, branched or unbranched alkyl or interrupted alkyl group. In an aspect (8), the disclosure provides the polymer of any of aspects (1)-(7), wherein at least one of R6, or R6′is an optionally substituted, branched or unbranched alkyl group. In an aspect (9), the disclosure provides the polymer of any of aspects (1)-(8), wherein R6′is

wherein each R10is independently, hydrogen and r, p, and q are integers of 2 or more. In an aspect (10), the disclosure provides the polymer of any of aspects (1)-(9), wherein each Z is S. In an aspect (11), the disclosure provides the polymer of any of aspects (1)-(10), wherein A and B are independently —C—H or N. In an aspect (12), the disclosure provides the polymer of any of aspects (1), (3)-(11), wherein the polymer is:

In an aspect (13), the disclosure provides the polymer of any of aspects (1)-(2), (4)-(11), wherein the polymer is:

In an aspect (14), the disclosure provides a method of making a polymer of any of aspects (1)-(13), wherein the method comprises reacting a first compound of structure 5′, 6′, 7′, or 8′:

with a second compound of structure 9′:

wherein each of G1and G2is a halogen or Sn(R8)3, where each R8is an alkyl, with the proviso that when G1is a halogen, G2is Sn(R8)3and when G2is a halogen, G1is Sn(R8)3. In an aspect (15), the disclosure provides the method of aspect (14), wherein the first compound is 5′ or 6′. In an aspect (16), the disclosure provides the method of aspect (14), wherein the first compound is 7′ or 8′. In an aspect (17), the disclosure provides the method of any of aspects (14)-(16), wherein each R1is:

wherein each R10is independently, hydrogen, an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, or a halide, an acyl halide, an acrylate, or a vinyl ether; and r, p, and q are integers of 2 or more. In an aspect (18), the disclosure provides the method of aspect (17), wherein each R10is hydrogen; p is an integer of 3 or more; and r and q are integers of 4 or more. In an aspect (19), the disclosure provides the method of aspect (18), wherein p is an integer of 6-8 and r and q are integers from 7-15. In an aspect (20), the disclosure provides the method of any of aspects (14)-(19), wherein at least one of R5, R5′, R6, or R6′is an optionally substituted, branched or unbranched alkyl or interrupted alkyl group. In an aspect (21), the disclosure provides the method of any of aspects (14)-(20), wherein at least one of R6, or R6′is an optionally substituted, branched or unbranched alkyl group. In an aspect (22), the disclosure provides the method of any of aspects (14)-(21), wherein R6′is

wherein each R10is independently, hydrogen and r, p, and q are integers of 2 or more. In an aspect (23), the disclosure provides the polymer of any of aspects (14)-(22), wherein each Z is S. In an aspect (24), the disclosure provides the polymer of any of aspects (14)-(23), wherein A and B are independently —C—H or N. In an aspect (25) the first compound is:

and
the second compound is:

In an aspect (26), the disclosure provides the method of aspect (25), wherein A and B are each N or C—H.

In an aspect (26) the first compound is:

and
the second compound is:

In an aspect (28), the disclosure provides the method of aspect (27), wherein A and B are each N or C—H. In an aspect (29), the disclosure provides the method of any of aspects (14)-(28), wherein the reaction occurs in the presence of a catalyst. In an aspect (30), the disclosure provides the method of any of aspects (14)-(29), wherein the reaction occurs via a Stille-type reaction. In an aspect (31), the disclosure provides the method of aspect (29) or (30), wherein the catalyst comprises a transition metal.

It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework for understanding the nature and character of the invention.

DETAILED DESCRIPTION

Before the present materials, articles, and/or methods are disclosed and described, it is to be understood that the aspects described below are not limited to specific compounds, synthetic methods, or uses as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

Throughout this specification, unless the context requires otherwise, the word “comprise,” or variations such as “comprises” or “comprising,” will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

“Optional” or “optionally” means that the subsequently described event or circumstance may or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.

Where a range of numerical values is recited herein, comprising upper and lower values, unless otherwise stated in specific circumstances, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the claims be limited to the specific values recited when defining a range. Further, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed.

When the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. When a numerical value or end-point of a range does not recite “about,” the numerical value or end-point of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.” It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

The term “alkyl group” as used herein may be a branched or unbranched saturated hydrocarbon group of 1 to 40 carbon atoms (or with a number of carbon atoms as defined by the nomenclature Cγ-Cζ, where γ and ζ are a numerical values with γ<ζ), such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, or tetradecyl, and the like. The alkyl group may be substituted or unsubstituted. The term “unsubstituted alkyl group” is defined herein as an alkyl group composed of just carbon and hydrogen. The term “substituted alkyl group” is defined herein as an alkyl group with one or more hydrogen atoms substituted with a group including, but not limited to, an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, or a halide, an acyl halide, an acrylate, or a vinyl ether. For example, the alkyl groups may be an alkyl hydroxy group, where any of the hydrogen atoms of the alkyl group are substituted with 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 composed of at least 3 carbon atoms, and in some embodiments from 3 to 20 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term cycloalkyl group also includes a heterocycloalkyl group, where at least one of the carbon atoms of the ring may be substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.

The term “interrupted alkyl group” as used herein is an alkyl group that has one or more non-carbon atoms, such as sulfur, oxygen, or nitrogen, in interspersed or interrupting the carbon chain, or has a carbon-carbon double or triple bond in the carbon chain. For example, —OCH3, —OCH2CH2—O—C2H5, —SCH2SC2H5, —C2H4OC2H4OCH3, —CH2CH═CHC2H5, —CHC═CC2H5, etc.

The term “aryl group” as used herein may be any carbon-based aromatic group, fused carbon-based aromatic group, including, but not limited to, benzene, naphthalene, etc. The term “aryl group” also includes “heteroaryl group,” meaning an aromatic ring composed of at least three carbon atoms that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy as defined herein. In some embodiments, the term “aryl group” may be limited to substituted or unsubstituted aryl and heteroaryl rings having from three to 30 carbon atoms.

The term “aralkyl” as used herein may be an aryl group having an alkyl group as defined above attached to the aryl group. An example of an aralkyl group may be a benzyl group.

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

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

The term “conjugated group” is defined as a linear, branched or cyclic group, or combination thereof, in which p-orbitals of the atoms within the group are connected via delocalization of electrons and wherein the structure may be described as containing alternating single and double or triple bonds and may further contain lone pairs, radicals, or carbenium ions. Conjugated cyclic groups may comprise one of or both aromatic and non-aromatic groups, and may comprise polycyclic or heterocyclic groups, such as diketopyrrolopyrrole. Ideally, conjugated groups are bound in such a way as to continue the conjugation between the thiophene moieties they connect. In some embodiments, “conjugated groups” may be limited to conjugated groups having three to 30 carbon atoms.

Disclosed are compounds, compositions, and components that may be used for, may be used in conjunction with, may be used in preparation of, or are products of the disclosed methods and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each may be specifically contemplated and described herein. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D may be disclosed, then even if each is not individually recited, each may be individually and collectively contemplated. Thus, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. Likewise, any subset or combination of these may be also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D. This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that may be performed it may be understood that each of these additional steps may be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination may be specifically contemplated and should be considered disclosed.

Compounds

High performance semiconducting fused thiophene polymers have previously been developed. Dialkylated tetrathienoacene (FT4) OSC copolymers can be deposited from a dichlorobenzene solution to yield ordered films with a short π-π distance of 3.76 angstroms and with field-effect hole mobilities that exceeds 0.4 cm2V−1s−1. These polymers enable simple transistor fabrication at relatively low temperatures, which is particularly important for the realization of large-area, mechanically flexible electronics. Advances in this field have led to targeted design of donor-acceptor based polymer systems that show improved mobilities. Some of the most popular donor-acceptor organic semiconducting copolymers are diketopyrrolopyrrole (DPP)-based copolymers. Hole mobility values reported are up to 12 cm2V−1s−1and electron mobility values reported are up to 3 cm2V−1s−1. Devices utilizing ambipolar polymer OTFTs containing donor-acceptor units have shown hole and electron mobility values of 6.30 cm2V−1s−1and 2.78 cm2V−1s−1, respectively. Yet these polymers have suffered from issues of stability and solubility. There is a continued, unmet need to find organic semiconducting polymer systems that are stable and easily processable while retaining the high mobilities necessary to make them useful in next generation electronics.

The present disclosure goes beyond DPP based systems and combines stable fused thiophene (FTx, where x describes the number thiophenes in the fused structure) donor groups:

with new acceptors. The new acceptor groups are based on the generic Arylthiadiazole structure:

wherein A and B are N or C—R7, and the variables Z, n, R1, R5, R5′, and R7are detailed below. For example, the acceptor group can be a benzothiadiazole (BTD) or thiadiazolopyridine (TDP):

The polymers described herein have the advantageous properties of employing high efficiency electron acceptors in a highly conjugated polymer structure, higher molecular weights than have previously been achieved, and increased solubility. In some embodiments, the polymers have molecular weights of from about 30-80 kDa or 40-60 kDa.

The fused thiophene moieties described herein are substituted with optionally substituted alkyl groups at the β-positions of the fused thiophene ring system. As used herein, an α-position of a fused thiophene ring system may be a non-fused carbon center that may be directly adjacent to the sulfur of a fused thiophene, while a β-position may be a non-fused carbon center that may be separated from the sulfur of the fused thiophene by an α-position. In the structures described herein, the α-positions are shown as being connected to the rest of the composition, while the β-positions are substituted with R1groups linked to the β-positions by alkyl chains.

One aspect comprises a polymer comprising a repeat unit of formula 5, 6, 7, or 8:

wherein each R1is independently, an optionally substituted, branched or unbranched alkyl or interrupted alkyl group, a halogen, an optionally substituted aryl or heteroaryl group, or an optionally substituted conjugated group; each R5, R5′, R6, R6′is independently, hydrogen, an optionally substituted, branched or unbranched alkyl or interrupted alkyl group, a halogen, an optionally substituted aryl or heteroaryl group, or an optionally substituted conjugated group; A and B are N or C—R7, where each R7is independently, hydrogen, halogen, or an optionally substituted, branched or unbranched alkyl or interrupted alkyl group; each Z is independently, NH, S, or O; n is an integer from 1-3; and m is an integer of 1 or more.

In some embodiments, at least one of R1, R5, R5′, R6, R6′, and R7may be a substituted or unsubstituted C4, C5, C6, C7, C8, C9, or C10or greater alkyl group. For example, at least one of R1, R5, R5′, R6, R6′, and R7may be an optionally substituted C4or greater alkyl group. In such embodiments, the optionally substituted C4or greater alkyl group may be a straight-chain alkyl group (e.g. butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or hexadecyl), a branched alkyl group (e.g. sec-butyl, neo-pentyl, 4-methylpentyl), or a substituted or unsubstituted C5or greater cycloalkyl group (e.g. cyclopentyl, cyclohexyl). In some embodiments, R1comprises a branched, optionally substituted alkyl group having a total number of carbons of 10, 12, 14, 16, 18, 20, 22, 25, or greater. In some embodiments, the branch point of the R1branched, optionally substituted alkyl is at C5, C6, C7, C8, C9, C10or greater. In some embodiments, at least one of R5, R5′, R6, or R6′comprises a branched, optionally substituted alkyl group having a total number of carbons of 10, 12, 14, 16, 18, 20, 22, 25, or greater. In some embodiments, the branch point of the R5, R5′, R6, or R6′branched, optionally substituted alkyl is at C5, C6, C7, C8, C9, C10or greater. In some embodiments, both R1and at least one of R5, R5′, R6, or R6′comprise branched, optionally substituted alkyl groups having a total number of carbons of 10, 12, 14, 16, 18, 20, 22, 25, or greater. In some embodiments, the branch point of both the R1and the at least one of R5, R5′, R6, or R6′branched, optionally substituted alkyl is at C5, C6, C7, C8, C9, C10or greater.

In particular, in some embodiments, both R1and at least one of R6, or R6′comprise branched, unsubstituted alkyl groups having a total number of carbons of 18, 20, 22, 25, or greater. In such embodiments, the branch point of both the R1and the at least one of R6, or R6′branched, unsubstituted alkyl is at C7, C8, C9, C10or greater. In substituted embodiments of R1, R5, R5′, R6, or R6′, each group may be substituted with one or more amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether moieties or any combination of two or more of these. The selection of R1, R5, R5′, R6, and R6′may depend on the end use of the moiety-containing composition. The methods described herein permit the synthesis of compositions having a wide variety of R1, R5, R5′, R6, and R6′substituents. Any functionality on a substituted alkyl group may also be protected in order to survive subsequent reaction steps.

wherein each R10is independently, hydrogen, an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, or a halide, an acyl halide, an acrylate, or a vinyl ether; r, p, q, and t are integers of 2 or more, and each a″ is independently CR10R10, N, O, S, or Si.

In some embodiments, n is an integer of 1 or greater. In some embodiments, n is an integer from 1 to 4, 1 to 3, or 1 to 2. In one aspect, m may be from 1 to 10,000, 1 to 9,000, 1 to 8,000, 1 to 7,000, 1 to 6,000, 1 to 5,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, 1 to 1,000, 1 to 500, 1 to 250, 1 to 100, 1 to 50, 1 to 25, 1 to 10, 25 to 1000, 25 to 500, 25 to 250, 50 to 1000, 50 to 500, or 50 to 250.

In some embodiments, A and B are each independently, N or C—R7. Each R7is hydrogen, halogen, or an optionally substituted, branched or unbranched alkyl or interrupted alkyl group. In some embodiments, A is N and B is C—R7. In some embodiments, B is N and A is C—R7. In some embodiments, A and B are both C—R7. In some embodiments, R7is a halogen, a C1-C3alkyl, or hydrogen. In some embodiments, R7is hydrogen.

The fused thiophene moieties described in 5-8 may have any number of fused rings above 3. For example, the fused thiophene moieties may be tetracyclic (6 & 8, n=1); pentacyclic (5 & 7, n=1), hexacyclic (6 & 8, n=2); or heptacyclic (5 & 7, n=2). The methods described herein permit the construction of fused thiophene moieties having any desired number of rings. In one aspect, for 5-8, n may be 1, 2, 3, 4, 5, 6, or 7.

An unexpected advantage of the embodied compounds described herein is that the presence of at least four long alkyl chains on the polymer provides improved mobility and processability properties. In some embodiments, the presence of two branched alkyl chains with branching points at the C4position or greater on the fused thiophene provides improved mobility and processability properties. In some embodiments, the presence of two branched alkyl chains with branching points at the C4position or greater on the fused thiophene in combination with two branched alkyl chains with branching points at the C4position or greater on the thiophene linkers provides improved mobility and processability properties. Additionally, the embodied polymers shown in 5-8 can have higher field effect hole mobility than current high performance polymers.

While it was expected that the large, branched alkyl chains would inhibit stacking or structured organization of the polymer, these potential issues were not observed. Rather, it is hypothesized that the embodied polymers provide superior properties because 1) since all branched alkyl chains are at least four carbons away from the main polymer backbone, there is no or very low steric effect from them to cause the twisting of the original planarity of the polymer backbone, which would interfere with the π-stacking of the polymer backbones, and 2) the existence of four large, nonpolar branched side chains in one polymer repeat unit significantly increases the solubility of these polymers and thus allow for an increase in the molecular weight of the polymers, which may result in an enhanced mobility over current high performance polymers. In some embodiments, the polymers have molecular weights of from about 30-80 kDa or 40-60 kDa.

One advantage of the increased solubility of the specific polymers disclosed herein is that they can be synthesized by advanced flow reactor techniques, which often can produce higher molecular weight polymers with tighter weight distribution. Additionally, in some non-limiting embodiments, the fused thiophenes (FT4) may be in liquid form at temperatures as low as 10° C., 5° C., 0° C., −5° C., or −10° C. Previously made polymers generally have limited solubility in various solvents and may be difficult to process, e.g., when preparing printed electronics, without negatively impacting electronic performance. The embodied FT4 monomers may satisfy these requirements since branched side-chain FT4 may be used to construct a larger conjugation system with less worry about solubility limitations.

Example embodiments of the compounds described herein may be found in TABLE 1:

TABLE 1#StructureR1R5R5′R615 or 6C4H8CHC8H17C10H21——H25 or 6C5H10CHC8H17C10H21——C4H935 or 6C6H12CHC8H17C10H21——H45 or 6C7H14CHC8H17C10H21——CH355 or 6C8H16CHC8H17C10H21——H65 or 6OC4H8CHC8H17C10H21——H75 or 6OC4H8CHC8H17C10H21——C5H10CHC8H17C10H2185 or 6C8H16CHC8H17C10H21——C6H12CHC8H17C10H2195 or 6C7H14CHC8H17C10H21——C7H14CHC8H17C10H21105 or 6C8H16CHC8H17C10H21——C8H16CHC8H17C10H21115 or 6C8H16CHC8H17C10H21——OC4H8CHC8H17C10H21127 or 8C8H16CHC8H17C10H21HHH137 or 8C6H12CHC8H17C10H21HHC4H9147 or 8C7H14CHC8H17C10H21C4H9HH157 or 8C8H16CHC8H17C10H21HHH167 or 8C5H10CHC8H17C10H21C6H12CHC8H17C10H21HH177 or 8C6H12CHC8H17C10H21HC7H14CHC8H17C10H21H187 or 8C7H14CHC8H17C10H21HHC7H14CHC8H17C10H21197 or 8C8H16CHC8H17C10H21C7H14CHC8H17C10H21HH207 or 8OC4H8CHC8H17C10H21HHH217 or 8C7H14CHC8H17C10H21HC7H14CHC8H17C10H21C7H14CHC8H17C10H21227 or 8C8H16CHC8H17C10H21C7H14CHC8H17C10H21HC7H14CHC8H17C10H21#R6′ZABn1OC4H8CHC8H17C10H21SNCH1 or 22C6H12CHC8H17C10H21NCHN1 or 23C7H14CHC8H17C10H21SCHCH1 or 24C8H16CHC8H17C10H21SNCH1 or 25C7H14CHC8H17C10H21SCHCH1 or 26HSCHCH1 or 27C4H9SNCH1 or 28HNNCH1 or 29CH3SCHCH1 or 210HNNN1 or 211HSCHN1 or 212C7H14CHC8H17C10H21SCHCH1 or 213OC4H8CHC8H17C10H21SCHCH1 or 214C7H14CHC8H17C10H2NCHCH1 or 215C7H14CHC8H17C10H21SNCH1 or 216C7H14CHC8H17C10H2NNCH1 or 217OC4H8CHC8H17C10H21SNCH1 or 218C8H16CHC8H17C10H21SCHCH1 or 219C6H12CHC8H17C10H21SCHCH1 or 220C7H14CHC8H17C10H21NNN1 or 221C8H16CHC8H17C10H21NNN1 or 222C5H10CHC8H17C10H21SCHN1 or 2

Methods

FIGS. 1 and 2provide synthetic routes to producing the arylthiadiazoles described herein. Using the synthetic route shown inFIG. 1, side chain R5groups may be introduced to the intervening thiophenes between the FT4 and the arylthiadiazole. The additional R5groups increase the solubility of these materials, and provide alternative synthetic designs that lend flexibility to the overall structure by not having to rely solely on the solubilizing power of the alkyl chain substituents of the fused thiophene moiety.FIG. 2provides an alternative synthetic route to a specific embodiment, DBrC8BC8C10TBTD.

In one aspect, compounds comprising the moiety 5-8 may be produced by reacting a compound comprising 9′ with a compound comprising 5′-8′. In one embodiment, the method for making a compound, such as 5-8, may be carried out by providing a monomer comprising a moiety of structure 9′:

wherein A, B, Z, R6, and R6′, are as listed above for 5-8 and G2is a halogen or Sn(R8)3, where each R8is an alkyl.

The method of making the compound may be further carried out by providing a fused thiophene compound comprising a moiety of structure 5′-8′

wherein n, R1, R5, R5′, and Z, are as defined above for formulas 5-8, and G1is a halogen or Sn(R8)3, where each R8is an alkyl, with the proviso that when G1is a halogen, G2is Sn(R8)3and when G2is a halogen, G1is Sn(R8)3. Each G1and G2may also be alternative groups, known or unknown, useful for Suzuki or Stille coupling.

Fused thiophene and oxidized fused thiophene oligomers and polymers may be prepared using methodologies similar to those used in making oligo- and poly(thiophenes) described above. For example, α,α′-dihydro fused thiophene moieties may be oxidatively oligomerized or polymerized using iron (III) compounds (e.g., FeCl3, Fe(acac)3), or may be brominated and coupled in an organomagnesium mediated reaction. The fused thiophene moieties and oxidized fused thiophene moieties described herein may be incorporated into other conjugated polymers such as, for example phenylene, vinylene, and acetylene copolymers, using coupling reactions familiar to the skilled artisan. The fused thiophene moieties and oxidized fused thiophene moieties described herein may be incorporated into other main chain and side chain polymers using techniques known in the art. It is contemplated that the fused thiophene compound may be oxidized prior to incorporation into an oligomer or polymer. In the alternative, the fused thiophene compound may be incorporated into the oligomer or polymer followed by oxidation.

Examples

The specific example materials, P2TBTD2TDC9BC8C10FT4 and PTBTDTDC9BC8C10FT4:

can be synthesized by the general procedure disclosed inFIG. 3. The monomers and catalyst materials are weighed into a flask and the solvent (m-xylene) added. The polymerization is then carried out at 125° C. for 1 h. The material is then precipitated, filtered, dried then extracted in a soxhlet to remove any residual monomers and catalyst species. Finally, the polymer is dissolved from the soxhlet, reprecipitated and dried under vacuum. The detailed synthetic procedure is given here for PTBTDTDC9BC8C10FT4 as an example.

Monomer 2,6-bis(trimethylstannyl)-3,7-bis(9-octylnonadecyl)thieno[3,2-b]thieno [2′,3′:4,5] thieno[2,3-d]thiophene 1.109 g (0.739 mmol, MW 1499.96), monomer 4,7-bis(5-bromothiophen-2-yl)benzo[c][1,2,5]thiadiazole 0.339 g (0.739 mmol, MW 458.2), and catalyst tris(dibenzylideneacetone)dipalladium(0) 13.5 mg (0.0148 mmol) with o-tolyl phosphine 17.5 mg (0.0575 mmol) are weighed into a round bottom flask (100 mL). m-Xylene (30 mL) and a stir bar are added. A condenser is fitted and the reaction mixture is lowered into a pre-heated oil bath at 125° C. and heated under nitrogen for 1 h. The mixture is then poured into a stirring mixture of methanol and acetylacetone (200 mL+200 mL). Hydrochloric acid (2 mL, 35% aq) is added and the mixture is stirred for 16 h. The mixture is filtered and the polymer placed into a soxhlet thimble. The polymer is extracted in a soxhlet apparatus with acetone (250 mL) for 24 h, then hexanes (250 mL) for 24 h. The polymer is then extracted from the soxhlet apparatus into chloroform (250 mL). The chloroform solution is poured into methanol (400 mL) with rapid stirring, followed by moderate stirring for 20 min. The polymer is then filtered from the mixture and dried under vacuum to give the product as a purple solid.

The molecular weights of embodied polymers are given in TABLE 2. These weights are determined using an Agilent GPC220 run at 200° C. with 1,2,4-trichlorobenzene as the mobile phase, flowing at 1 mL/min. The column used is a Resipore 300×7.5 mm column. A refractive index detector, previously calibrated against polystyrene standards in the range 10000 to 240000, is used to determine the molecular weights.

TABLE 2MnMwPDIPTBTDTDC9BC8C10FT438000735001.94P2TBTD2TDC9BC8C10FT4470001444003.07
The UV-visible spectra of these two polymers are shown inFIG. 4.