# Patent

## Title
Polymeric semiconductors and related devices

## Abstract

The present teachings relate to new semiconducting polymers including an optionally substituted naphtho[1,2-d:5,6-d]bis[1,2,3]thiadiazole moiety, an optionally substituted naphtho[2,1-d:6,5-d]bis[1,2,3]thiadiazole moiety, or a chalcogen analog thereof. The present polymers can be used to prepare thin film semiconductor components which can be incorporated into various electronic, optical, and optoelectronic devices.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to and the benefit of U.S. Provisional Patent Application Ser. No. 62/191,413 filed on Jul. 12, 2015, the disclosure of which is incorporated by reference herein in its entirety.


BACKGROUND
A new generation of optoelectronic devices such as organic thin film transistors (OTFTs), organic light emitting transistors (OLETs), organic light emitting diodes (OLEDs), printable circuits, organic photovoltaic (OPV) devices, electrochemical capacitors, and sensors are built upon organic semiconductors as their active components. To enable high device efficiencies such as large charge carrier mobilities (μ) needed for transistor/circuit operations, or efficient exciton formation/splitting necessary for OLED/OPV operations, it is desirable that both p-type and n-type organic semiconductor materials are available. Furthermore, these organic semiconductor-based devices should exhibit satisfactory stability in ambient conditions and should be processable in a cost-effective manner.
Several p- and n-channel molecular semiconductors have achieved acceptable device performance and stability. For example, OTFTs based on acenes and oligothiophenes (p-channel) and perylenes (n-channel) exhibit carrier mobilities (μ) >0.5 cm2/Vs in ambient conditions. However, molecular semiconductors typically are less easily processable via printing methodologies than polymeric semiconductors due to solution viscosity requirements.
Accordingly, the art desires new polymeric semiconductors, particularly those having good stability, processing properties, and/or charge transport characteristics in ambient conditions.
SUMMARY
In light of the foregoing, the present teachings provide organic semiconducting polymers that can address various deficiencies and shortcomings of the prior art, including those outlined above. Also provided are associated devices and related methods for the preparation and use of these polymers. The present polymers can exhibit properties such as excellent charge transport characteristics in ambient conditions, chemical stability, low-temperature processability, satisfactory solubility in common solvents, and processing versatility (e.g., printability). As a result, field effect devices such as thin film transistors that incorporate one or more of the present polymers as the semiconductor layer can exhibit high performance in ambient conditions, for example, demonstrating one or more of large electron mobilities, low threshold voltages, and high current on-off ratios. Similarly, other organic semiconductor-based devices such as OPVs, OLETs, and OLEDs can be fabricated efficiently using the polymeric materials described herein.
Generally, the present teachings provide polymers that include a repeating unit (M1) comprising a moiety of the formula (I) or (II):




wherein X is a chalcogen, and R1 can be H or a substituent. In some embodiments, the repeating unit (M1) can comprise a moiety of the formula (III) or (IV)





where R1 is as defined herein.

In certain embodiments, the polymer is a homopolymer including only repeating units M1. In other embodiments, the polymer also includes at least one other repeating unit M2 that does not include any moiety of the formula (I) or (II). Such M2 unit can be selected from:




wherein pi-2, Ar, Z, m, m′, m′′, p, and p′ are as defined herein.

The present teachings also provide methods of preparing such polymers and semiconductor materials, as well as various compositions, composites, and devices that incorporate the polymers and semiconductor materials disclosed herein.
The foregoing as well as other features and advantages of the present teachings will be more fully understood from the following figures, description, examples, and claims.



BRIEF DESCRIPTION OF DRAWINGS
It should be understood that the drawings described below are for illustration purpose only. The drawings are not necessarily to scale, with emphasis generally being placed upon illustrating the principles of the present teachings. The drawings are not intended to limit the scope of the present teachings in any way.
FIG. 1 illustrates four different configurations of thin film transistors: a) bottom-gate top contact, b) bottom-gate bottom-contact, c) top-gate bottom-contact, and d) top-gate top-contact; each of which can be used to incorporate one or more polymers of the present teachings, particularly as the channel (semiconductor) materials.
FIG. 2 illustrates a representative structure of a bulk-heterojunction organic photovoltaic device (also known as a solar cell), which can incorporate one or more polymers of the present teachings as the donor and/or acceptor materials.
FIG. 3 illustrates a representative structure of an organic light-emitting device which can incorporate one or more polymers of the present teachings as electron-transporting and/or emissive and/or hole-transporting materials.
FIG. 4 illustrates a zoomed in region of the 1H NMR spectrum of a monomer unit based upon a naphtho[1,2-d:5,6-d]bis[1,2,3]thiadiazole moiety according to the present teachings.
FIG. 5 illustrates a zoomed in region of the 1H NMR spectrum of another monomer unit based upon a naphtho[1,2-d:5,6-d]bis[1,2,3]thiadiazole moiety according to the present teachings.
FIG. 6 illustrates the frontier molecular orbitals of a naphtho[1,2-d:5,6-d]bis[1,2,3]thiadiazole moiety and a naphtho[2,1-d:6,5-d]bis[1,2,3]thiadiazole moiety, respectively, as compared to the isomeric naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole moiety known in the art (top).
FIG. 7 illustrates the frontier molecular orbitals of a monomer based upon a naphtho[1,2-d:5,6-d]bis[1,2,3]thiadiazole moiety or a naphtho[2,1-d:6,5-d]bis[1,2,3]thiadiazole moiety coupled with flanking thienyl groups as compared to a corresponding monomer including the isomeric naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole moiety (top).



DETAILED DESCRIPTION
The present teachings provide organic semiconductor materials that include organic semiconducting polymers and associated compositions, composites, and/or devices. Polymers of the present teachings can exhibit semiconductor behavior such as high carrier mobility and/or good current modulation characteristics in a field-effect device, light absorption/charge separation in a photovoltaic device, and/or charge transport/recombination/light emission in a light-emitting device. In addition, the present polymers can possess certain processing advantages such as solution-processability and/or good stability (for example, air stability) in ambient conditions. The polymers of the present teachings can be used to prepare either p-type or n-type semiconductor materials, which in turn can be used to fabricate various organic electronic articles, structures and devices, including field-effect transistors, unipolar circuitries, complementary circuitries, photovoltaic devices, and light emitting devices.
Accordingly, one aspect of the present teachings provides polymers having semiconducting activity and semiconductor materials prepared from these polymers. More specifically, the polymers can be A-B copolymers of a monomer A (also referred to herein as the first repeating unit, M1) that comprises an optionally substituted naphtho[1,2-d:5,6-d]bis[1,2,3]thiadiazole group, an optionally substituted naphtho[2,1-d:6,5-d]bis[1,2,3]thiadiazole group, or a chalcogen analog thereof (i.e., where the sulfur atom in the thiadiazole ring is replaced with O, Se, or Te), and a monomer B (also referred to herein as the second repeating unit, M2) that includes one or more groups which either by themselves or together with monomer A provide a pi-conjugated system. The monomer B typically includes an aromatic or otherwise highly conjugated cyclic (carbocyclic or heterocyclic) core, where such cyclic core can be optionally substituted or functionalized with one or more electron-withdrawing or electron-donating groups. The pairing of monomers A and B, and any additional functionalization on either monomer can be affected by one or more of the following considerations: 1) the electron-withdrawing capability for semiconductor processing in air and stable charge transport operation; 2) modulation of the majority carrier type depending on the electronic structure of monomers A and B; 3) regiochemistry of the polymerization possibly affording regioregular polymers; 4) the core planarity and linearity of the polymer chain; 5) the capability of additional functionalization of the π-conjugated core; 6) the potential for increased solubility of the polymer for solution processing; 7) achieving strong π-π interactions/intermolecular electronic coupling; and 8) bandgap modulation via electron donor-acceptor coupling of electron-poor (acceptor) and electron-rich (donor) A-B or B-A repeating units. The resulting polymers and related methods can be employed to enhance the performance of an associated device (e.g., an organic field effect transistor, a light-emitting transistor, a solar cell, or the like).
Throughout the application, where compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings also consist essentially of, or consist of, the recited components, and that the processes of the present teachings also consist essentially of, or consist of, the recited process steps.
In the application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components and can be selected from a group consisting of two or more of the recited elements or components. Further, it should be understood that elements and/or features of a composition, an apparatus, or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present teachings, whether explicit or implicit herein.
The use of the terms “include,” “includes”, “including,” “have,” “has,” or “having” should be generally understood as open-ended and non-limiting unless specifically stated otherwise.
The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. In addition, where the use of the term “about” is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term “about” refers to a ±10% variation from the nominal value unless otherwise indicated or inferred.
It should be understood that the order of steps or order for performing certain actions is immaterial so long as the present teachings remain operable. Moreover, two or more steps or actions may be conducted simultaneously.
As used herein, a “p-type semiconductor material” or a “donor” material refers to a semiconductor material, for example, an organic semiconductor material, having holes as the majority current or charge carriers. In some embodiments, when a p-type semiconductor material is deposited on a substrate, it can provide a hole mobility in excess of about 10−5 cm2/Vs. In the case of field-effect devices, a p-type semiconductor also can exhibit a current on/off ratio of greater than about 10.
As used herein, an “n-type semiconductor material” or an “acceptor” material refers to a semiconductor material, for example, an organic semiconductor material, having electrons as the majority current or charge carriers. In some embodiments, when an n-type semiconductor material is deposited on a substrate, it can provide an electron mobility in excess of about 10−5 cm2/Vs. In the case of field-effect devices, an n-type semiconductor also can exhibit a current on/off ratio of greater than about 10.
As used herein, “mobility” refers to a measure of the velocity with which charge carriers, for example, holes (or units of positive charge) in the case of a p-type semiconductor material and electrons (or units of negative charge) in the case of an n-type semiconductor material, move through the material under the influence of an electric field. This parameter, which depends on the device architecture, can be measured using a field-effect device or space-charge limited current measurements.
As used herein, a compound can be considered “ambient stable” or “stable at ambient conditions” when a transistor incorporating the compound as its semiconducting material exhibits a carrier mobility that is maintained at about its initial measurement when the compound is exposed to ambient conditions, for example, air, ambient temperature, and humidity, over a period of time. For example, a compound can be described as ambient stable if a transistor incorporating the compound shows a carrier mobility that does not vary more than 20% or more than 10% from its initial value after exposure to ambient conditions, including, air, humidity and temperature, over a 3 day, 5 day, or 10 day period. In addition, a polymer can be considered ambient stable if the optical absorption of the corresponding film does not vary more than 20% (preferably, does not vary more than 10%) from its initial value after exposure to ambient conditions, including air, humidity and temperature, over a 3 day, 5 day, or 10 day period.
As used herein, fill factor (FF) is the ratio (given as a percentage) of the actual maximum obtainable power, (Pm or Vmp*Jmp), to the theoretical (not actually obtainable) power, (Jsc*Voc). Accordingly, FF can be determined using the equation:

FF=(Vmp*Jmp)/(Jsc*Voc)

where Jmp and Vmp represent the current density and voltage at the maximum power point (Pm), respectively, this point being obtained by varying the resistance in the circuit until J*V is at its greatest value; and Jsc and Voc represent the short circuit current and the open circuit voltage, respectively. Fill factor is a key parameter in evaluating the performance of solar cells. Commercial solar cells typically have a fill factor of about 60% or greater.

As used herein, the open-circuit voltage (Voc) is the difference in the electrical potentials between the anode and the cathode of a device when there is no external load connected.
As used herein, the power conversion efficiency (PCE) of a solar cell is the percentage of power converted from incident light to electrical power. The PCE of a solar cell can be calculated by dividing the maximum power point (Pm) by the input light irradiance (E, in W/m2) under standard test conditions (STC) and the surface area of the solar cell (Ac in m2). STC typically refers to a temperature of 25° C. and an irradiance of 1000 W/m2 with an air mass 1.5 (AM 1.5) spectrum.
As used herein, a component (such as a thin film layer) can be considered “photoactive” if it contains one or more compounds that can absorb photons to produce excitons for the generation of a photocurrent.
As used herein, “solution-processable” refers to compounds (e.g., polymers), materials, or compositions that can be used in various solution-phase processes including spin-coating, printing (e.g., inkjet printing, gravure printing, offset printing and the like), spray coating, electrospray coating, drop casting, dip coating, and blade coating.
As used herein, a “polymeric compound” (or “polymer”) refers to a molecule including a plurality of one or more repeating units connected by covalent chemical bonds. A polymeric compound can be represented by the general formula:

*M*

wherein M is the repeating unit or monomer. The polymeric compound can have only one type of repeating unit as well as two or more types of different repeating units. When a polymeric compound has only one type of repeating unit, it can be referred to as a homopolymer. When a polymeric compound has two or more types of different repeating units, the term “copolymer” or “copolymeric compound” can be used instead. For example, a copolymeric compound can include repeating units

*Ma* and *Mb*,

where Ma and Mb represent two different repeating units. Unless specified otherwise, the assembly of the repeating units in the copolymer can be head-to-tail, head-to-head, or tail-to-tail. In addition, unless specified otherwise, the copolymer can be a random copolymer, an alternating copolymer, or a block copolymer. For example, the general formula:

*Max-Mby*

can be used to represent a copolymer of Ma and Mb having x mole fraction of Ma and y mole fraction of Mb in the copolymer, where the manner in which comonomers Ma and Mb is repeated can be alternating, random, regiorandom, regioregular, or in blocks. In addition to its composition, a polymeric compound can be further characterized by its degree of polymerization (n) and molar mass (e.g., number average molecular weight (Mn) and/or weight average molecular weight (Mw) depending on the measuring technique(s)).

As used herein, “halo” or “halogen” refers to fluoro, chloro, bromo, and iodo.
As used herein, “oxo” refers to a double-bonded oxygen (i.e., ═O).
As used herein, “alkyl” refers to a straight-chain or branched saturated hydrocarbon group. Examples of alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and iso-propyl), butyl (e.g., n-butyl, iso-butyl, sec-butyl, tert-butyl), pentyl groups (e.g., n-pentyl, iso-pentyl, neopentyl), hexyl groups, and the like. In various embodiments, an alkyl group can have 1 to 40 carbon atoms (i.e., C1-40 alkyl group), for example, 1-20 carbon atoms (i.e., C1-20 alkyl group). In some embodiments, an alkyl group can have 1 to 6 carbon atoms, and can be referred to as a “lower alkyl group.” Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and iso-propyl), and butyl groups (e.g., n-butyl, iso-butyl, sec-butyl, ten-butyl). In some embodiments, alkyl groups can be substituted as described herein. An alkyl group is generally not substituted with another alkyl group, an alkenyl group, or an alkynyl group.
As used herein, “haloalkyl” refers to an alkyl group having one or more halogen substituents. At various embodiments, a haloalkyl group can have 1 to 40 carbon atoms (i.e., C1-40 haloalkyl group), for example, 1 to 20 carbon atoms (i.e., C1-20 haloalkyl group). Examples of haloalkyl groups include CF3, C2F5, CHF2, CH2F, CCl3, CHCl2, CH2Cl, C2Cl5, and the like. Perhaloalkyl groups, i.e., alkyl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., CF3 and C2F5), are included within the definition of “haloalkyl.” For example, a C1-40 haloalkyl group can have the formula —CzH2z+1−tX0t, where X0, at each occurrence, is F, Cl, Br or I, z is an integer in the range of 1 to 40, and t is an integer in the range of 1 to 81, provided that t is less than or equal to 2z+1. Haloalkyl groups that are not perhaloalkyl groups can be substituted as described herein.
As used herein, “alkoxy” refers to —O-alkyl group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), t-butoxy, pentoxyl, hexoxyl groups, and the like. The alkyl group in the —O-alkyl group can be substituted as described herein.
As used herein, “alkylthio” refers to an —S— alkyl group. Examples of alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio (e.g., n-propylthio and isopropylthio), t-butylthio, pentylthio, hexylthio groups, and the like. The alkyl group in the —S-alkyl group can be substituted as described herein.
As used herein, “alkenyl” refers to a straight-chain or branched alkyl group having one or more carbon-carbon double bonds. Examples of alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl groups, and the like. The one or more carbon-carbon double bonds can be internal (such as in 2-butene) or terminal (such as in 1-butene). In various embodiments, an alkenyl group can have 2 to 40 carbon atoms (i.e., C2-40 alkenyl group), for example, 2 to 20 carbon atoms (i.e., C2-20 alkenyl group). In some embodiments, alkenyl groups can be substituted as described herein. An alkenyl group is generally not substituted with another alkenyl group, an alkyl group, or an alkynyl group.
As used herein, “alkynyl” refers to a straight-chain or branched alkyl group having one or more triple carbon-carbon bonds. Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, and the like. The one or more triple carbon-carbon bonds can be internal (such as in 2-butyne) or terminal (such as in 1-butyne). In various embodiments, an alkynyl group can have 2 to 40 carbon atoms (i.e., C2-40 alkynyl group), for example, 2 to 20 carbon atoms (i.e., C2-20 alkynyl group). In some embodiments, alkynyl groups can be substituted as described herein. An alkynyl group is generally not substituted with another alkynyl group, an alkyl group, or an alkenyl group.
As used herein, “heteroatom” refers to an atom of any element other than carbon or hydrogen and includes, for example, nitrogen, oxygen, silicon, sulfur, phosphorus, and selenium.
As used herein, a “cyclic moiety” can include one or more (e.g., 1-6) carbocyclic or heterocyclic rings. In embodiments where the cyclic moiety is a “polycyclic moiety,” the “polycyclic moiety” can include two or more rings fused to each other (i.e., sharing a common bond) and/or connected to each other via a spiro atom. The cyclic moiety can be a cycloalkyl group, a heterocycloalkyl group, an aryl group, or a heteroaryl group (i.e., can include only saturated bonds, or can include one or more unsaturated bonds regardless of aromaticity), and can be optionally substituted as described herein. In embodiments where the cyclic moiety is a “monocyclic moiety,” the “monocyclic moiety” can include a 3-20 membered carbocyclic or heterocyclic ring. A monocyclic moiety can include a C6-20 aryl group (e.g., C6-14 aryl group) or a 5-20 membered heteroaryl group (e.g., 5-14 membered heteroaryl group), each of which can be optionally substituted as described herein.
As used herein, “cycloalkyl” refers to a non-aromatic carbocyclic group including cyclized alkyl, alkenyl, and alkynyl groups. In various embodiments, a cycloalkyl group can have 3 to 20 carbon atoms, for example, 3 to 14 carbon atoms (i.e., C3-14 cycloalkyl group). A cycloalkyl group can be monocyclic (e.g., cyclohexyl) or polycyclic (e.g., containing fused, bridged, and/or Spiro ring systems), where the carbon atoms are located inside or outside of the ring system. Any suitable ring position of the cycloalkyl group can be covalently linked to the defined chemical structure. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcaryl, adamantyl, and spiro[4.5]decanyl groups, as well as their homologs, isomers, and the like. In some embodiments, cycloalkyl groups can be substituted as described herein.
As used herein, “cycloheteroalkyl” refers to a non-aromatic cycloalkyl group that contains at least one ring heteroatom selected from O, S, Se, N, P, and Si (e.g., O, S, and N), and optionally contains one or more double or triple bonds. A cycloheteroalkyl group can have 3 to 20 ring atoms, for example, 3 to 14 ring atoms (i.e., 3-14 membered cycloheteroalkyl group). One or more N, P, S, or Se atoms (e.g., N or S) in a cycloheteroalkyl ring may be oxidized (e.g., morpholine N-oxide, thiomorpholine S-oxide, thiomorpholine S,S-dioxide). In some embodiments, nitrogen or phosphorus atoms of cycloheteroalkyl groups can bear a substituent, for example, a hydrogen atom, an alkyl group, or other substituents as described herein. Cycloheteroalkyl groups can also contain one or more oxo groups, such as oxopiperidyl, oxooxazolidyl, dioxo-(1H,3H)-pyrimidyl, oxo-2(1H)-pyridyl, and the like. Examples of cycloheteroalkyl groups include, among others, morpholinyl, thiomorpholinyl, pyranyl, imidazolidinyl, imidazolinyl, oxazolidinyl, pyrazolidinyl, pyrazolinyl, pyrrolidinyl, pyrrolinyl, tetrahydrofuranyl, tetrahydrothiophenyl, piperidinyl, piperazinyl, and the like. In some embodiments, cycloheteroalkyl groups can be substituted as described herein.
As used herein, “aryl” refers to an aromatic monocyclic hydrocarbon ring system or a polycyclic ring system in which two or more aromatic hydrocarbon rings are fused (i.e., having a bond in common with) together or at least one aromatic monocyclic hydrocarbon ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings. An aryl group can have 6 to 22 carbon atoms in its ring system (e.g., C6-14 aryl group), which can include multiple fused rings. In some embodiments, a polycyclic aryl group can have from 8 to 22 carbon atoms. Any suitable ring position of the aryl group can be covalently linked to the defined chemical structure. Examples of aryl groups having only aromatic carbocyclic ring(s) include phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), anthracenyl (tricyclic), phenanthrenyl (tricyclic), pentacenyl (pentacyclic) and like groups. Examples of polycyclic ring systems in which at least one aromatic carbocyclic ring is fused to one or more cycloalkyl and/or cycloheteroalkyl rings include, among others, benzo derivatives of cyclopentane (i.e., an indanyl group, which is a 5,6-bicyclic cycloalkyl/aromatic ring system), cyclohexane (i.e., a tetrahydronaphthyl group, which is a 6,6-bicyclic cycloalkyl/aromatic ring system), imidazoline (i.e., a benzimidazolinyl group, which is a 5,6-bicyclic cycloheteroalkyl/aromatic ring system), and pyran (i.e., a chromenyl group, which is a 6,6-bicyclic cycloheteroalkyl/aromatic ring system). Other examples of aryl groups include benzodioxanyl, benzodioxolyl, chromanyl, indolinyl groups, and the like. In some embodiments, aryl groups can be substituted as described herein. In some embodiments, an aryl group can have one or more halogen substituents, and can be referred to as a “haloaryl” group. Perhaloaryl groups, i.e., aryl groups where all of the hydrogen atoms are replaced with halogen atoms (e.g., —C6F5), are included within the definition of “haloaryl.” In certain embodiments, an aryl group is substituted with another aryl group and can be referred to as a biaryl group. Each of the aryl groups in the biaryl group can be substituted as disclosed herein.
As used herein, “arylalkyl” refers to an -alkyl-aryl group, where the arylalkyl group is covalently linked to the defined chemical structure via the alkyl group. An arylalkyl group is within the definition of a —Y—C6-14 aryl group, where Y is as defined herein. An example of an arylalkyl group is a benzyl group (—CH2—C6H5). An arylalkyl group can be optionally substituted, i.e., the aryl group and/or the alkyl group, can be substituted as disclosed herein.
As used herein, “heteroaryl” refers to an aromatic monocyclic ring system containing at least one ring heteroatom selected from oxygen (O), nitrogen (N), sulfur (S), silicon (Si), and selenium (Se) or a polycyclic ring system where at least one of the rings present in the ring system is aromatic and contains at least one ring heteroatom. Polycyclic heteroaryl groups include two or more heteroaryl rings fused together and monocyclic heteroaryl rings fused to one or more aromatic carbocyclic rings, non-aromatic carbocyclic rings, and/or non-aromatic cycloheteroalkyl rings. A heteroaryl group, as a whole, can have, for example, 5 to 22 ring atoms and contain 1-5 ring heteroatoms (i.e., 5-20 membered heteroaryl group). The heteroaryl group can be attached to the defined chemical structure at any heteroatom or carbon atom that results in a stable structure. Generally, heteroaryl rings do not contain O—O, S—S, or S—O bonds. However, one or more N or S atoms in a heteroaryl group can be oxidized (e.g., pyridine N-oxide, thiophene S-oxide, thiophene S,S-dioxide). Examples of heteroaryl groups include, for example, the 5- or 6-membered monocyclic and 5-6 bicyclic ring systems shown below:




where T is O, S, NH, N-alkyl, N-aryl, N-(arylalkyl) (e.g., N-benzyl), SiH2, SiH(alkyl), Si(alkyl)2, SiH(arylalkyl), Si(arylalkyl)2, or Si(alkyl)(arylalkyl). Examples of such heteroaryl rings include pyrrolyl, furyl, thienyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl, imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, indolyl, isoindolyl, benzofuryl, benzothienyl, quinolyl, 2-methylquinolyl, isoquinolyl, quinoxalyl, quinazolyl, benzotriazolyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxadiazolyl, benzoxazolyl, cinnolinyl, 1H-indazolyl, 2H-indazolyl, indolizinyl, isobenzofuyl, naphthyridinyl, phthalazinyl, pteridinyl, purinyl, oxazolopyridinyl, thiazolopyridinyl, imidazopyridinyl, furopyridinyl, thienopyridinyl, pyridopyrimidinyl, pyridopyrazinyl, pyridopyridazinyl, thienothiazolyl, thienoxazolyl, thienoimidazolyl groups, and the like. Further examples of heteroaryl groups include 4,5,6,7-tetrahydroindolyl, tetrahydroquinolinyl, benzothienopyridinyl, benzofuropyridinyl groups, and the like. In some embodiments, heteroaryl groups can be substituted as described herein.

Polymers of the present teachings can include a “divalent group” defined herein as a linking group capable of forming a covalent bond with two other moieties. For example, polymers of the present teachings can include a divalent C1-20 alkyl group (e.g., a methylene group), a divalent C2-20 alkenyl group (e.g., a vinylyl group), a divalent C2-20 alkynyl group (e.g., an ethynylyl group), a divalent C6-14 aryl group (e.g., a phenylyl group); a divalent 3-14 membered cycloheteroalkyl group (e.g., a pyrrolidylyl), and/or a divalent 5-14 membered heteroaryl group (e.g., a thienylyl group).
The electron-donating or electron-withdrawing properties of several hundred of the most common substituents, reflecting all common classes of substituents have been determined, quantified, and published. The most common quantification of electron-donating and electron-withdrawing properties is in terms of Hammett σ values. Hydrogen has a Hammett σ value of zero, while other substituents have Hammett σ values that increase positively or negatively in direct relation to their electron-withdrawing or electron-donating characteristics. Substituents with negative Hammett σ values are considered electron-donating, while those with positive Hammett σ values are considered electron-withdrawing. See Lange's Handbook of Chemistry, 12th ed., McGraw Hill, 1979, Table 3-12, pp. 3-134 to 3-138, which lists Hammett σ values for a large number of commonly encountered substituents and is incorporated by reference herein.
It should be understood that the term “electron-accepting group” can be used synonymously herein with “electron acceptor” and “electron-withdrawing group”. In particular, an “electron-withdrawing group” (“EWG”) or an “electron-accepting group” or an “electron-acceptor” refers to a functional group that draws electrons to itself more than a hydrogen atom would if it occupied the same position in a molecule. Examples of electron-withdrawing groups include, but are not limited to, halogen or halo (e.g., F, Cl, Br, I), —NO2, —CN, —NC, —S(R0)2+, —N(R0)3+, —SO3H, —SO2R0, —SO3R0, —SO2NHR0, —SO2N(R0)2, —COOH, —COR0, —COOR0, —CONHR0, —CON(R0)2, C1-40 haloalkyl groups, C6-14 aryl groups, and 5-14 membered electron-poor heteroaryl groups; where R0 is a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C1-20 alkoxy group, a C6-14 aryl group, a C3-14 cycloalkyl group, a 3-14 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group, each of which can be optionally substituted as described herein. For example, each of the C1-20 alkyl group, the C2-20 alkenyl group, the C2-20 alkynyl group, the C1-20 haloalkyl group, the C1-20 alkoxy group, the C6-14 aryl group, the C3-14 cycloalkyl group, the 3-14 membered cycloheteroalkyl group, and the 5-14 membered heteroaryl group can be optionally substituted with 1-5 small electron-withdrawing groups such as F, Cl, Br, —NO2, —CN, —NC, —S(R0)2+, —N(R0)3+, —SO3H, —SO2R0, —SO3R0, —SO2NHR0, —SO2N(R0)2, —COOH, —COR0, —COOR0, —CONHR0, and —CON(R0)2.
It should be understood that the term “electron-donating group” can be used synonymously herein with “electron donor”. In particular, an “electron-donating group” or an “electron-donor” refers to a functional group that donates electrons to a neighboring atom more than a hydrogen atom would if it occupied the same position in a molecule. Examples of electron-donating groups include —OH, —OR0, —NH2, —NHR0, —N(R0)2, and 5-14 membered electron-rich heteroaryl groups, where R0 is a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C6-14 aryl group, or a C3-14 cycloalkyl group.
Various unsubstituted heteroaryl groups can be described as electron-rich (or π-excessive) or electron-poor (or π-deficient). Such classification is based on the average electron density on each ring atom as compared to that of a carbon atom in benzene. Examples of electron-rich systems include 5-membered heteroaryl groups having one heteroatom such as furan, pyrrole, and thiophene; and their benzofused counterparts such as benzofuran, benzopyrrole, and benzothiophene. Examples of electron-poor systems include 6-membered heteroaryl groups having one or more heteroatoms such as pyridine, pyrazine, pyridazine, and pyrimidine; as well as their benzofused counterparts such as quinoline, isoquinoline, quinoxaline, cinnoline, phthalazine, naphthyridine, quinazoline, phenanthridine, acridine, and purine. Mixed heteroaromatic rings can belong to either class depending on the type, number, and position of the one or more heteroatom(s) in the ring. See Katritzky, A. R and Lagowski, J. M., Heterocyclic Chemistry (John Wiley & Sons, New York, 1960).
At various places in the present specification, substituents of monomers A and B are disclosed in groups or in ranges. It is specifically intended that the description include each and every individual subcombination of the members of such groups and ranges. For example, the term “C1-6 alkyl” is specifically intended to individually disclose C1, C2, C3, C4, C5, C6, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, C2-C6, C2-C5, C2-C4, C2-C3, C3-C6, C3-C5, C3-C4, C4-C6, C4-C5, and C5-C6 alkyl. By way of other examples, an integer in the range of 0 to 40 is specifically intended to individually disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40, and an integer in the range of 1 to 20 is specifically intended to individually disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Additional examples include that the phrase “optionally substituted with 1-5 substituents” is specifically intended to individually disclose a chemical group that can include 0, 1, 2, 3, 4, 5, 0-5, 0-4, 0-3, 0-2, 0-1, 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, and 4-5 substituents.
Polymers described herein can contain an asymmetric atom (also referred as a chiral center) and some of the polymers can contain two or more asymmetric atoms or centers, which can thus give rise to optical isomers (enantiomers) and diastereomers (geometric isomers). The present teachings include such optical isomers and diastereomers, including their respective resolved enantiomerically or diastereomerically pure isomers (e.g., (+) or (−) stereoisomer) and their racemic mixtures, as well as other mixtures of the enantiomers and diastereomers. In some embodiments, optical isomers can be obtained in enantiomerically enriched or pure form by standard procedures known to those skilled in the art, which include, for example, chiral separation, diastereomeric salt formation, kinetic resolution, and asymmetric synthesis. The present teachings also encompass cis- and trans-isomers of polymers containing alkenyl moieties (e.g., alkenes, azo, and imines). It also should be understood that the polymers of the present teachings encompass all possible regioisomers in pure form and mixtures thereof. It may be possible to separate such isomers, for example, using standard separation procedures known to those skilled in the art, for example, column chromatography, thin-layer chromatography, simulated moving-bed chromatography, and high-performance liquid chromatography. However, mixtures of regioisomers can be used similarly to the uses of each individual regioisomer of the present teachings.
It is specifically contemplated that the depiction of one regioisomer includes any other regioisomers and any regioisomeric mixtures unless specifically stated otherwise.
As used herein, a “leaving group” (“LG”) refers to a charged or uncharged atom (or group of atoms) that can be displaced as a stable species as a result of, for example, a substitution or elimination reaction. Examples of leaving groups include, but are not limited to, halogen (e.g., Cl, Br, I), azide (N3), thiocyanate (SCN), nitro (NO2), cyanate (CN), water (H2O), ammonia (NH3), and sulfonate groups (e.g., OSO2—R, wherein R can be a C1-10 alkyl group or a C6-14 aryl group each optionally substituted with 1-4 groups independently selected from a C1-10 alkyl group and an electron-withdrawing group) such as tosylate (toluenesulfonate, OTs), mesylate (methanesulfonate, OMs), brosylate (p-bromobenzenesulfonate, OBs), nosylate (4-nitrobenzenesulfonate, ONs), and triflate (trifluoromethanesulfonate, OTf).
In various embodiments, the polymers of the present teachings include a first repeating unit (M1) comprising a moiety of the formula:




wherein:

X is selected from the group consisting of O, S, Se, and Te;

R1, at each occurrence, independently can be selected from the group consisting of H, halogen, —CN, NO2, R2, -L-R3, OH, OR2, OR3, NH2, NHR2, N(R2)2, NHR3, NR2R3, N(R3)2, SH, SR2, SR3, S(O)2OH, —S(O)2OR2, —S(O)2OR3, C(O)H, C(O)R2, C(O)R3, C(O)OH, C(O)OR2, C(O)OR3, C(O)NH2, C(O)NHR2, C(O)N(R2)2, C(O)NHR3, C(O)NR2R3, C(O)N(R3)2, SiH3, SiH(R2)2, SiH2(R2), and Si(R2)3, wherein L is selected from the group consisting of a divalent C1-40 alkyl group, a divalent C2-40 alkenyl group, a divalent C1-40 haloalkyl group, and a covalent bond; R2 is selected from the group consisting of a C1-40 alkyl group, a C2-40 alkenyl group, a C2-40 alkynyl group, and a C1-40 haloalkyl group; and R3 is selected from the group consisting of a C3-10 cycloalkyl group, a C6-14 aryl group, a C6-14 haloaryl group, a 3-12 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group, each of which optionally is substituted with 1-5 substituents selected from the group consisting of a halogen, —CN, NO2, R2, OR2, and SR2; and wherein the polymer can have a degree of polymerization (n) ranging from 3 to 1,000.

For example, in various embodiments, R1, at each occurrence, independently can be selected from the group consisting of H, halogen, —CN, —NO2, R2, OR2, and SR2, wherein R2, at each occurrence, independently can be selected from the group consisting of a C1-40 alkyl group, a C1-40 alkenyl group, and a C1-40 haloalkyl group. In certain embodiments, R1, at each occurrence, independently can be selected from H, F, Cl, CN, a C3-40 alkyl group, a C3-40 alkoxy group, a C3-40 haloalkyl group, and a C3-40 alkenyl group, where each of the C3-40 alkyl group, the C3-40 alkoxy group, the C3-40 haloalkyl group, and the C3-40 alkenyl group can be linear or branched. In particular embodiments, both R1 can be H. In other embodiments, each R1 independently can be F or Cl.
In some embodiments, the present compound is a polymer having one or more repeating units M1, where each M1 includes at least one moiety of the formula (I) or (II). In some embodiments, other than the moiety of formula (I) or (II), repeating units M1 can include one or more spacers (Sp) which can be either non-cyclic (Z) or cyclic, particularly monocyclic (Ar) or polycyclic (pi-2), which together with the moiety of the formula (I) or (II) provide a pi-extended conjugated group. For example, M1 can be selected from the group consisting of:




wherein:

R1 is as defined herein;

pi-2 is an optionally substituted conjugated polycyclic moiety;

Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;

Z is a conjugated noncyclic linker;

m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0; and

p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

To illustrate, the polycyclic conjugated moiety, pi-2, can be an optionally substituted C8-26 aryl group or 8-26 membered heteroaryl group. For example, pi-2 can have a planar and pi-extended conjugated cyclic core which can be optionally substituted as disclosed herein. Examples of suitable cyclic cores include naphthalene, anthracene, tetracene, pentacene, perylene, pyrene, coronene, fluorene, indacene, indenofluorene, and tetraphenylene, as well as their analogs in which one or more carbon atoms can be replaced with a heteroatom such as O, S, Si, Se, N, or P.
In certain embodiments, pi-2 can be selected from:






















wherein:

Ra is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;

Rb is selected from the group consisting of H, R, and -L′-Rf;

Rc is H or R;

Rd is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L′-Rf;

Re is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and Rf;

Rf is a C6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;

L′ is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and

R is selected from the group consisting of a C1-40 alkyl group, a C1-40 haloalkyl group, a C2-40 alkenyl group, and a C2-40 alkynyl group.

The monocyclic conjugated moiety, Ar, at each occurrence, independently can be an optionally substituted 5- or 6-membered (hetero)aryl group. For example, Ar can be selected from the group consisting of a phenyl group, a thienyl group, a selenophene group, a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, a furyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a pyrrolyl group, a triazolyl group, a tetrazolyl group, a pyrazolyl group, an imidazolyl group, a pyridyl group, a pyrimidyl group, a pyridazinyl group, and a pyrazinyl group, each of which optionally can be substituted with 1-4 R5 groups independently selected from a halogen, CN, a C1-40 alkyl group, a C1-40 haloalkyl group, a C1-40 alkoxy group, and a C1-40 alkylthio group.
By way of example, each Ar in (Ar)m, (Ar)m′, and/or (Ar)m′′ that is present (i.e., when m, m′, and/or m′′ is 1, 2, 3, 4, 5 or 6) can be represented by:




where each W independently can be selected from N, CH, and CR4, wherein R4 can be selected from F, Cl, —CN, R2, OR2, SR2, C(O)R2, OC(O)R2, and C(O)OR2, where R2 is as defined herein. To illustrate further, (Ar)m, (Ar)m′, or (Ar)m′′ when present can be selected from:

















where, for example, each R4 independently is selected from F, Cl, CN, R2, OR2, and SR2, where R2 is a linear or branched C1-40 alkyl or haloalkyl group.

The conjugated noncyclic linker, Z, can include one or more double or triple bonds. For example, Z can be a divalent ethenyl group (i.e., having one double bond), a divalent ethynyl group (i.e., having one tripe bond), a C4-40 alkenyl or alkynyl group that includes two or more conjugated double or triple bonds, or some other linear or branched conjugated systems that can include heteroatoms such as Si, N, P, and the like. In certain embodiments, Z can be selected from:




wherein R4 is as defined herein. In particular embodiments, Z can be selected from:





In preferred embodiments, the present polymer includes a repeating unit M1 selected from the group consisting of:




where Ar, R1, Z, pi-2, m, m′, p, and p′ are as defined herein.

In certain embodiments, the present polymer can be a homopolymer including only identical repeating units M1. In other embodiments, the polymer can be a copolymer including two or more different repeating units M1. In yet other embodiments, the polymer can be a copolymer including at least one repeating unit M1 and at least one other repeating unit M2 that does not include any moiety of formula (I) or (II). Such M2 units can include one or more non-cyclic (Z), monocyclic (Ar), and/or polycyclic (pi-2) conjugated linkers, which together provide a pi-extended conjugated group. For example, M2 can be selected from:




wherein m′′ is 1, 2, 3, 4, 5 or 6; and pi-2, Ar, Z, m, m′, m′′, p, and p′ are as defined herein.

To illustrate, in certain embodiments, M2 can have the formula:




wherein m′′ is selected from 1, 2, 3, or 4; and Ar is as defined herein. For example, M2 can be selected from the group consisting of:

















where, for example, each R4 independently is selected from F, Cl, CN, R2, OR2, and SR2, where R2 is a linear or branched C1-40 alkyl or haloalkyl group.

In other embodiments, M2 can have the formula:




wherein pi-2 can be selected from:























wherein:

Ra is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;

Rb is selected from the group consisting of H, R, and -L′-Rf;

Rc is H or R;

Rd is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L′-Rf;

Re is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and Rf;

Rf is a C6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;

L′ is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and

R is selected from the group consisting of a C1-40 alkyl group, a C1-40 haloalkyl group, a C2-40 alkenyl group, and a C2-40 alkynyl group.

In yet other embodiments, M2 can have the formula:




wherein Ar, pi-2, m and m′ are as defined herein. Preferably, (Ar)m and (Ar)m′ are selected from:





where R4 is as defined herein, and pi-2 is selected from:























wherein:

Ra is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;

Rb is selected from the group consisting of H, R, and -L′-Rf;

Rc is H or R;

Rd is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L′-Rf;

Re is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and Rf;

Rf is a C6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;

L′ is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and

R is selected from the group consisting of a C1-40 alkyl group, a C1-40 haloalkyl group, a C2-40 alkenyl group, and a C2-40 alkynyl group.

In other embodiments, M2 can have a formula selected from:




wherein m, m′ and m′′ independently are 1, 2, 3 or 4; and Ar, pi-2 and Z are as defined herein.

In preferred embodiments, the present polymers are copolymers of M1 and at least one M2, where M2 is selected from:




where pi-2, Ar, m, m′, and m′′′ are as defined herein.

To illustrate, certain embodiments of the present polymers can be represented by the formula:




where n is an integer ranging from 3 to 1,000. Such polymers can be obtained by copolymerizing a precursor of M1 represented by





with a precursor of M2 represented by





where U and V are complementary polymerizing groups. Alternatively, the same polymers can be obtained by copolymerizing a precursor of M1 represented by





with a precursor of M2 represented by





Preferably, (Ar)m and (Ar)m′ are selected from:





where R4 is selected from a C1-40 alkyl group, a C1-40 alkoxy group, and a C1-40 haloalkyl group; and pi-2 is selected from:





where Ra and Rd are as defined herein.

For the various polymers described above, the degree of polymerization (n) can be an integer between 3 and 1,000. In some embodiments, n can be 4-1,000, 5-1,000, 6-1,000, 7-1,000, 8-1,000, 9-1,000, or 10-1,000. For example, n can be 8-500, 8-400, 8-300, or 8-200. In certain embodiments, n can be 8-100. In particular embodiments, the molecular weight of the polymer can be at least 5,000 g/mol, preferably at least 10,000 g/mol.
Embodiments of the present compounds including M1 and at least one M2 can have the two units repeated in a random or alternating manner, and the mole fraction of the two units can be between about 0.05 and about 0.95. For example, the respective mole fractions (x and y) of the two units can be between about 0.1 and about 0.9, between about 0.2 and about 0.8, between about 0.3 and about 0.7, between about 0.4 and about 0.6, or between about 0.45 and about 0.55. In certain embodiments, the present polymers can include the same mole fraction of the first unit as the second unit (i.e., x=y=0.5).
Monomers according to the present teachings can be prepared using synthetic routes described in the examples hereinbelow. Other monomers according to the present teachings can be commercially available, known in the literature, or can be prepared from readily prepared intermediates by employing standard synthetic methods and procedures known to those skilled in the art. Standard synthetic methods and procedures for the preparation of organic molecules and functional group transformations and manipulations can be readily obtained from the relevant scientific literature or from standard textbooks in the field. It will be appreciated that where typical or preferred process conditions (i.e., reaction temperatures, times, mole ratios of reactants, solvents, pressures, etc.) are given, other process conditions can also be used unless otherwise stated. Optimum reaction conditions can vary with the particular reactants or solvent used, but such conditions can be determined by one skilled in the art by routine optimization procedures. Those skilled in the art of organic synthesis will recognize that the nature and order of the synthetic steps presented can be varied for the purpose of optimizing the formation of the compounds described herein.
The processes described herein can be monitored according to any suitable method known in the art. For example, product formation can be monitored by spectroscopic means, such as nuclear magnetic resonance spectroscopy (NMR, e.g., 1H or 13C), infrared spectroscopy (IR), optical absorption/emission spectroscopy (e.g., UV-visible), mass spectrometry (MS), or by chromatography such as high pressure liquid chromatography (HPLC), gas chromatography (GC), gel-permeation chromatography (GPC), or thin layer chromatography (TLC).
The reactions or the processes described herein can be carried out in suitable solvents which can be readily selected by one skilled in the art of organic synthesis. Suitable solvents typically are substantially nonreactive with the reactants, intermediates, and/or products at the temperatures at which the reactions are carried out, i.e., temperatures that can range from the solvent's freezing temperature to the solvent's boiling temperature. A given reaction can be carried out in one solvent or a mixture of more than one solvent. Depending on the particular reaction step, suitable solvents for a particular reaction step can be selected.
The homopolymerization of M1 and the copolymerization of M1 and M2 can be achieved via various reactions known to those skilled in the art, including procedures analogous to those described in Yamamoto, J. Organomet. Chem., 653: 195-199 (2002); Walton et al., Polymer Chemistry (Fred J. Davis ed. 2004), p. 158-187; and Galbrecht et al., Macromolecular Rapid Communications, 28(4): 387-394 (2007), the entire disclosure of each of which is incorporated by reference herein for all purposes. In particular, Stille coupling or Suzuki coupling reactions can be used to prepare polymeric compounds according to the present teachings with high molecular weights and in high yields (≧75%) and purity, as confirmed by 1H NMR spectra, elemental analysis, and/or GPC measurements. Scheme 1 below outlines several exemplary reactions that can be used to polymerize M1 by itself or copolymerize M1 with M2. It should be understood that the polymerizable groups (e.g., SnR3, BR2, MgX, ZnX, and Br, where X is a halogen and R is an alkyl group) can be reversed between M1 and M2. Analogous reactions can be used to couple a moiety of formula (I) or (II) with Ar, pi-2, and/or Z moieties to provide a repeating unit M1 including such Ar, pi-2, and/or Z moieties in addition to the moiety of formula (I) or (II).




Without wishing to be bound by any particular theory, it is believed that polymers of the present teachings that have a regioregular polymeric backbone can lead to higher molecular weights, a more π-conjugated structure and, consequently better charge transport efficiencies. Accordingly, in preparing the present polymers, the present teachings can include isolating a particular average molecular weight fractions, and/or enriching and/or isolating a particular stereoisomer of M1 and/or M2 that has two or more stereoisomers.
Certain embodiments disclosed herein can be stable in ambient conditions (“ambient stable”) and soluble in common solvents. As used herein, a polymer can be considered electrically “ambient stable” or “stable at ambient conditions” when the carrier mobility or the reduction-potential of the polymer is maintained at about its initial measurement when the polymer is exposed to ambient conditions, for example, air, ambient temperature, and humidity, over a period of time. For example, a polymer according to the present teachings can be described as ambient stable if its carrier mobility or redox potential does not vary more than 20% or more than 10% from its initial value after exposure to ambient conditions, including, air, humidity and temperature, over a 3 day, 5 day, or 10 day period. In addition, a polymer can be considered ambient stable if the optical absorption of the corresponding film does not vary more than 20% (preferably, does not vary more than 10%) from its initial value after exposure to ambient conditions, including air, humidity and temperature, over a 3 day, 5 day, or 10 day period.
Without wishing to be bound by any particular theory, it is believed that if n-channel transport is desired, the strong electron-depleted electronic structure enabled by M1 copolymerized with a strong electron-depleted M2 repeating unit, together with the regioregular highly π-conjugated polymeric backbone of the present polymers, can make the present polymers ambient-stable n-channel semiconductor materials without requiring additional π-core functionalization (i.e., core substitution of the naphthalene moiety) with strong electron-withdrawing functionalities. If large light absorption (extinction coefficient) is desired, the present polymers can be provided with a highly π-conjugated polymeric backbone and by having the M1 unit copolymerized with an electron-donating M2 comonomer to enable a push-pull structure. If an ambipolar polymer is desired, for example in light-emitting transistor applications, the present polymers can have a highly π-conjugated polymeric backbone comprising a copolymer of M1 and an electron-neutral or electron-donating (electron-rich) M2 unit.
OTFTs based on the present polymers can have long-term operability and continued high-performance in ambient conditions. For example, OTFTs based on certain embodiments of the present polymers can maintain satisfactory device performance in highly humid environment. Certain embodiments of the present polymers also can exhibit excellent thermal stability over a wide range of annealing temperatures. Photovoltaic devices can maintain satisfactory power conversion efficiencies over an extended period of time.
Compounds, particularly polymers, disclosed herein can be soluble in various common organic solvents. As used herein, a compound can be considered soluble in a solvent when at least 0.1 mg of the compound can be dissolved in 1 mL of the solvent. Examples of common organic solvents include petroleum ethers; acetonitrile; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as acetone, and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane, bis(2-methoxyethyl) ether, diethyl ether, di-isopropyl ether, and t-butyl methyl ether; alcohols such as methanol, ethanol, butanol, and isopropyl alcohol; aliphatic hydrocarbons such as hexanes; esters such as methyl acetate, ethyl acetate, methyl formate, ethyl formate, isopropyl acetate, and butyl acetate; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; halogenated aliphatic and aromatic hydrocarbons such as dichloromethane, chloroform, ethylene chloride, chlorobenzene, dichlorobenzene, and trichlorobenzene; and cyclic solvents such as cyclopentanone, cyclohexanone, and 2-methypyrrolidone. The present polymers can have room temperature solubilities in conventional organic solvents such as xylene, dichlorobenzene (DCB), and other chlorinated hydrocarbons (CHCs) as high as 60 g/L.
The compounds described herein can be dissolved, dispersed or suspended in a single solvent or mixture of solvents to provide a composition suitable for solution processing techniques. In preferred embodiments, the solvent can be selected from the group consisting of chlorobenzene, dichlorobenzene (o-dichlorobenzene, m-dichlorobenzene, p-orobenzene, or mixtures thereof), trichlorobenzene, benzene, toluene, chloroform, dichloromethane, dichloroethane, xylenes, α,α,α-trichlorotoluene, methyl naphthalene (e.g., 1-methylnaphthalene, 2-methylnaphthalene, or mixtures thereof), chloronaphthalene (e.g., 1-chloronaphthalene, 2-chloronaphthalene, or mixtures thereof), and mixtures thereof. The present polymers can be fabricated into various articles of manufacture using solution processing techniques in addition to other more expensive processes such as vapor deposition. Various solution-phase processing techniques have been used with organic electronics. Common solution-phase processing techniques include, for example, spin coating, slot coating, doctor blading, drop-casting, zone casting, dip coating, blade coating, or spraying. Another example of solution-phase processing technique is printing. As used herein, “printing” includes a noncontact process such as inkjet printing, microdispensing and the like, and a contact process such as screen-printing, gravure printing, offset printing, flexographic printing, lithographic printing, pad printing, microcontact printing and the like.
Polymers of the present teachings can be used to prepare semiconductor materials (e.g., compositions and composites), which in turn can be used to fabricate various articles of manufacture, structures, and devices. In some embodiments, semiconductor materials incorporating one or more polymers of the present teachings can exhibit n-type semiconductor activity, ambipolar activity, light absorption, and light emission.
The present teachings, therefore, further provide methods of preparing a semiconductor material. The methods can include preparing a composition that includes one or more polymers disclosed herein dissolved or dispersed in a liquid medium such as a solvent or a mixture of solvents, depositing the composition on a substrate to provide a semiconductor material precursor, and processing (e.g., heating) the semiconductor precursor to provide a semiconductor material (e.g., a thin film semiconductor) that includes a polymer disclosed herein. In various embodiments, the liquid medium can be an organic solvent, an inorganic solvent such as water, or combinations thereof. In some embodiments, the composition can further include one or more additives independently selected from viscosity modulators, detergents, dispersants, binding agents, compatibilizing agents, curing agents, initiators, humectants, antifoaming agents, wetting agents, pH modifiers, biocides, and bacteriostats. For example, surfactants and/or polymers (e.g., polystyrene, polyethylene, poly-alpha-methyl styrene, polyisobutene, polypropylene, polymethylmethacrylate, and the like) can be included as a dispersant, a binding agent, a compatibilizing agent, and/or an antifoaming agent. In some embodiments, the depositing step can be carried out by printing, including inkjet printing and various contact printing techniques (e.g., screen-printing, gravure printing, offset printing, pad printing, lithographic printing, flexographic printing, and microcontact printing). In other embodiments, the depositing step can be carried out by spin coating, drop-casting, zone casting, dip coating, blade coating, or spraying.
Various articles of manufacture including electronic devices, optical devices, and optoelectronic devices, such as thin film semiconductors, field effect transistors (e.g., thin film transistors), photovoltaics, photodetectors, organic light emitting devices such as organic light emitting diodes (OLEDs) and organic light emitting transistors (OLETs), complementary metal oxide semiconductors (CMOSs), complementary inverters, diodes, capacitors, sensors, D flip-flops, rectifiers, and ring oscillators, that make use of the polymers disclosed herein are within the scope of the present teachings as are methods of making the same. The present polymers can offer processing and operation advantages in the fabrication and/or the use of these devices. For example, articles of manufacture such as the various devices described herein can include a composite having a semiconductor material of the present teachings and a substrate component and/or a dielectric component. The substrate component can be selected from doped silicon, an indium tin oxide (ITO), ITO-coated glass, ITO-coated polyimide or other plastics, aluminum or other metals alone or coated on a polymer or other substrate, a doped polythiophene, and the like. The dielectric component can be prepared from inorganic dielectric materials such as various oxides (e.g., SiO2, Al2O3, HfO2), organic dielectric materials such as various polymeric materials (e.g., polycarbonate, polyester, polystyrene, polyhaloethylene, polyacrylate), and self-assembled superlattice/self-assembled nanodielectric (SAS/SAND) materials (e.g., described in Yoon, M-H. et al., PNAS, 102 (13): 4678-4682 (2005), the entire disclosure of which is incorporated by reference herein), as well as hybrid organic/inorganic dielectric materials (e.g., described in U.S. patent application Ser. No. 11/642,504, the entire disclosure of which is incorporated by reference herein). In some embodiments, the dielectric component can include the crosslinked polymer blends described in U.S. patent application Ser. Nos. 11/315,076, 60/816,952, and 60/861,308, the entire disclosure of each of which is incorporated by reference herein. The composite also can include one or more electrical contacts. Suitable materials for the source, drain, and gate electrodes include metals (e.g., Au, Al, Ni, Cu), transparent conducting oxides (e.g., ITO, IZO, ZITO, GZO, GIO, GITO), and conducting polymers (e.g., poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), polyaniline (PANI), polypyrrole (PPy)). One or more of the composites described herein can be embodied within various organic electronic, optical, and optoelectronic devices such as organic thin film transistors (OTFTs), specifically, organic field effect transistors (OFETs), as well as sensors, capacitors, unipolar circuits, complementary circuits (e.g., inverter circuits), and the like.
Other articles of manufacture in which polymers of the present teachings are useful are photovoltaics or solar cells. Polymers of the present teachings can exhibit broad optical absorption and/or a tuned redox properties and bulk carrier mobilities, making them desirable for such applications. Accordingly, the polymers described herein can be used as an acceptor (n-type) semiconductor or a donor (p-type) semiconductor depending on the nature of the M2 unit in a photovoltaic design, which includes an adjacent p-type or n-type semiconductor material, respectively, that forms a p-n junction. The polymers can be in the form of a thin film semiconductor, which can be deposited on a substrate to form a composite. Exploitation of polymers of the present teachings in such devices is within the knowledge of a skilled artisan.
Accordingly, another aspect of the present teachings relates to methods of fabricating an organic field effect transistor that incorporates a semiconductor material of the present teachings. The semiconductor materials of the present teachings can be used to fabricate various types of organic field effect transistors including top-gate top-contact capacitor structures, top-gate bottom-contact capacitor structures, bottom-gate top-contact capacitor structures, and bottom-gate bottom-contact capacitor structures. FIG. 1 illustrates the four common types of OFET structures: (a) bottom-gate top-contact structure, (b) bottom-gate bottom-contact structure, (c) top-gate bottom-contact structure, and (d) top-gate top-contact structure. As shown in FIG. 1, an OFET can include a dielectric layer (e.g., shown as 8, 8′, 8′′, and 8′′ in FIGS. 1a, 1b, 1c, and 1d, respectively), a semiconductor/channel layer (e.g., shown as 6, 6′, 6′′, and 6′′ in FIGS. 1a, 1b, 1c, and 1d, respectively), a gate contact (e.g., shown as 10, 10′, 10′′, and 10′′ in FIGS. 1a, 1b, 1c, and 1d, respectively), a substrate (e.g., shown as 12, 12′, 12′′, and 12′′ in FIGS. 1a, 1b, 1c, and 1d, respectively), and source and drain contacts (e.g., shown as 2, 2′, 2′′, 2′′, 4, 4′, 4′′, and 4′′ in FIGS. 1a, 1b, 1c, and 1d, respectively).
In certain embodiments, OTFT devices can be fabricated with the present polymers on doped silicon substrates, using SiO2 as the dielectric, in top-contact geometries. In particular embodiments, the active semiconductor layer which incorporates at least a polymer of the present teachings can be deposited at room temperature or at an elevated temperature. In other embodiments, the active semiconductor layer which incorporates at least one polymer of the present teachings can be applied by spin-coating or printing as described herein. For top-contact devices, metallic contacts can be patterned on top of the films using shadow masks.
In certain embodiments, OTFT devices can be fabricated with the present polymers on plastic foils, using polymers as the dielectric, in top-gate bottom-contact geometries. In particular embodiments, the active semiconducting layer which incorporates at least a polymer of the present teachings can be deposited at room temperature or at an elevated temperature. In other embodiments, the active semiconducting layer which incorporates at least a polymer of the present teachings can be applied by spin-coating or printing as described herein. Gate and source/drain contacts can be made of Au, other metals, or conducting polymers and deposited by vapor-deposition and/or printing.
Similarly, another aspect of the present teachings relates to methods of fabricating an organic light-emitting transistor, an organic light-emitting diode (OLED), or an organic photovoltaic device that incorporates one or more semiconductor materials of the present teachings. FIG. 2 illustrates a representative structure of a bulk-heterojunction organic photovoltaic device (also known as solar cell) which can incorporate one or more polymers of the present teachings as the donor and/or acceptor materials. As shown, a representative solar cell generally includes a substrate 20 (e.g., glass), an anode 22 (e.g., ITO), a cathode 26 (e.g., aluminium or calcium), and an active layer 24 between the anode and the cathode which can incorporate one or more polymers of the present teachings as the electron donor (p-channel) and/or electron acceptor (n-channel) materials. FIG. 3 illustrates a representative structure of an OLED which can incorporate one or more polymers of the present teachings as electron-transporting and/or emissive and/or hole-transporting materials. As shown, an OLED generally includes a substrate 30 (not shown), a transparent anode 32 (e.g., ITO), a cathode 40 (e.g., metal), and one or more organic layers which can incorporate one or more polymers of the present teachings as hole-transporting (n-channel) (layer 34 as shown) and/or emissive (layer 36 as shown) and/or electron-transporting (p-channel) materials (layer 38 as shown).
The following examples are provided to illustrate further and to facilitate the understanding of the present teachings and are not in any way intended to limit the invention. It will be appreciated that where typical or preferred process conditions (i.e., reaction temperatures, times, mole ratios of reactants, solvents, pressures, etc.) are given, other process conditions can also be used unless otherwise stated. Optimum reaction conditions can vary with the particular reactants or solvent used, but such conditions can be determined by one skilled in the art by routine optimization procedures. Those skilled in the art of organic synthesis will recognize that the nature and order of the synthetic steps presented can be varied for the purpose of optimizing the formation of the compounds described herein.
Example 1




Scheme 2 above illustrates an exemplary synthetic route to compound 5 which, after bromination, can be used to provide various semiconducting polymers. In the instant example, the brominated building block 6 was coupled with thiophene moieties to provide the polymer P1.
Step 1: Compound 1 (10 g, 35 mmol) was combined with concentrated HNO3 (100 mL) and the resulting mixture was stirred at room temperature overnight. The reaction mixture was then poured over ice ( ̃200 g), and the resulting yellow precipitate was collected by filtration, rinsed with water, and then stirred in boiling CHCl3 for 2 hours before filtration at room temperature. The collected solid was dried under vacuum to yield a yellow powder (6.8 g, 52%). 1H NMR (400 MHz. DMSO-d6): 8.12 (d, J=9.2 Hz, 2H), 7.90 (d, J=8.8 Hz, 2H).
Step 2: Compound 2 (5 g, 13.3 mmol) was suspended in DMF under N2. Benzyl mercaptan (4 mL, 34 mmol) and K2CO3 (2.25 g, 16.3 mmol) were added and the reaction mixture was heated to 80° C. overnight. The solution was cooled to room temperature before it was poured over ice-cooled brine (200 mL) and the precipitate was isolated via filtration. The product was further purified by column chromatography on silica gel (Hexanes:DCM=1:1, v/v), leading to a yellow-orange powder (1.1 g, 18%). 1H NMR (400 MHz. CDCl3): 7.72 (d, J=9.2 Hz, 2H), 7.55 (d, J=8.8 Hz, 2H), 7.27 (m, br, 10H), 4.22 (s, 4H).
Step 3: Compound 3 (700 mg, 1.51 mmol) was suspended in a mixture of ethanol (20 mL) and acetic acid (5 mL) in a 2-neck round-bottom flask equipped with a condenser. The mixture was brought to a gentle reflux before iron powder (1.18 g, 1.5 mmol) was added, followed immediately by iron(III) chloride hexahydrate (121 mg, 0.42 mmol). The mixture was heated at reflux overnight, then cooled and concentrated. The concentrated residue was stirred in water (50 mL) and filtered. The brown precipitate (502 mg, 82%) was dried and used in the next step without further purification. 1H NMR (400 MHz. CDCl3): 7.83 (d, J=8.8, 2H), 7.37 (d, J=11.6 Hz, 2H), 7.21 (m, br, 10H), 4.10 (s, 4H), 3.92 (s, 4H).
Step 4: Compound 4 (490 mg, 1.24 mmol) was suspended in water (20 mL), 12M HCl (4 mL), and AcOH (4 mL). Sodium nitrite (514 mg, 7.45 mmol) was then added slowly at room temperature. The reaction was stirred at room temperature overnight and then poured into water. The precipitate was filtered and then rinsed with water (3×50 mL) to yield a brown powder (170 mg, 56%). 1H NMR (400 MHz, CDCl3): 9.45 (d, J=8.8 Hz, 2H), 8.45 (d, J=9.2 Hz, 2H).
Step 5 and Step 6: Compound 5 (170 mg, 0.69 mmol) was dissolved in oleum (12 mL). NBS (272 mg, 1.53 mmol) was added in one portion and the reaction mixture was heated to 80° C. overnight. The solution was then cooled to RT and poured over 50 mL ice water. Product was filtered and rinsed with water (2×50 mL) to yield a crude black-brown powder (235 mg, 85%) which was used directly in the next step without further purification. Compound 6 (183 mg crude, 0.45 mmol), 4-(2-decyltetradecyl)-2-trimethylstannyl thiophene (585 mg, 1.00 mmol), Pd2dba3 (16.5 mg, 0.02 mmol), and tri(2-furyl)phosphine (16.7 mg, 0.07 mmol) were added to an air free flask which was then pumped and backfilled with argon for 4 times. Anhydrous THF (12 mL) was added via syringe and the solution was stirred at 85° C. for 16 h. Upon cooling to room temperature, the reaction mixture was concentrated in vacuo. The product was isolated via column chromatography on silica gel (Hexanes:CHCl3=4:1, v/v) as a yellow powder ( ̃5 mg, 7A), and the mono-coupling product (7B) was also isolated (31 mg).
Compound 7A: 1H NMR (400 MHz, CDCl3): 9.60 (s, 2H) 7.57 (s, 2H) 7.12 (s, 2H), 2.67 (d, J=6.4 Hz, 4H), 1.71 (m, br, 2H), 1.25 (m, br, 80H), 0.87 (t, J=6.4 Hz, 12H). Compound 7B: 1H NMR (400 MHz, CDCl3): 9.61 (s, 1H) 9.41 (d, J=9.2, 1H) 8.39 (d, J=8.8, 1H), 7.56 (s, 1H), 7.13 (s, 1H), 2.66 (d, J=6.9 Hz, 2H), 1.70 (m, br, 1H), 1.24 (m, br, 40H), 0.86 (t, J=6.4 Hz, 6H), FIG. 4 and FIG. 5 illustrate zoom-in regions of the 1H NMR spectra of compound 7A and compound 7B, respectively.
Example 2




Scheme 3 above illustrates the synthesis of another exemplary polymer of the present teachings, P2, from building block 6. Specifically, compound 6 (26.0 mg, 0.064 mmol), 5,5′-bis(trimethylstannyl)-2,2′-bithiophene (9) (30.8 mg, 0.064 mmol), Pd2dba3 (1.2 mg, 0.0013 mmol), tol3P (3.2 mg, 0.011 mmol) were placed in a Schlenk flask. The system was reduced to vacuum and backfilled with argon three times, before anhydrous chlorobenzene (5 mL) was added via syringe. The resulting mixture was warmed and stirred at 90° C. for 18 h. The reaction was cooled to room temperature and methanol (20 mL) was added upon stirring. The precipitate was collected by filtration, washed with methanol, and dried in vacuum, leading to a dark solid as the polymer P2 (11 mg).
Example 3




Scheme 4 above illustrates the synthesis of yet another exemplary polymer of the present teachings, P3, from building block 6. Specifically, compound 6 (28.5 mg, 0.071 mmol), benzodithiophene tin reagent 10 (79.8 mg, 0.071 mmol), Pd2dba3 (1.3 mg, 0.0014 mmol), tol3P (3.5 mg, 0.011 mmol) were placed in a Schlenk flask. The system was reduced to vacuum and backfilled with argon three times, before anhydrous chlorobenzene (5 mL) was added via syringe. The resulting mixture was warmed and stirred at 90° C. for 18 h. The reaction was cooled to room temperature and methanol (20 mL) was added upon stirring. The precipitate was collected by filtration, washed with methanol, and dried in vacuum, leading to a dark solid as the polymer P3 (16 mg).
Example 4




Scheme 5 above provides an alternative synthetic route to building block 5 and its brominated analog 6. The latter can be used to prepare polymers according to the present teachings, for example, via Suzuki or Stille coupling. a. Sulfone synthesis. Lisitsyn, V. N. et al. Zhurnal Organicheskoi Khimii (1985), 21(1), 161-4. b. Nitration c. Reduction. Reduction. de Lucchi, Ottorino et al From Organic Reactions (Hoboken, N.J., United States), 40, 1991. Alway, F. J. et al. Journal of the American Chemical Society (1902), 24, 1052-1060. d. Diazotation. Mo, Fanyang et al. Organic & Biomolecular Chemistry (2013), 11(10), 1582-1593. e. Bromination. De Almeida et al. Current Green Chemistry (2014), 1(2), 94-107.
Example 5




The isomer of building block 5 can be prepared according to Scheme 6 above. The final product can be brominated and used to prepare polymers according to the present teachings, for example, via Suzuki or Stille coupling. Synthetic procedures used above have been used in the following references: a. Reduction. Jagadeesh, Rajenahally V. et al Science 342(6162), 1073-1076; 2013. b. Suphurization. Bandgar, B. P. et al From Sulfur Letters, 24(3), 123-126; 2000. c. Alkylation. Gogoi, Prasanta et al Tetrahedron, 70(41), 7484-7489; 2014. d. Amination. Nadri, Shirin et al From Tetrahedron Letters, 55(30), 4098-4101.
Example 6




Scheme 7 above provides an alternative synthesis to the synthetic route described in Example 5. Synthetic procedures used above have been used in the following references: a. Bromination/Dehalogenation. Letizia, Joseph A. et al From Chemistry—A European Journal, 16(6), 1911-1928, S1911/1-S1911/9; 2010. b. Amination. Harkins, Seth B. and Peters, Jonas C. From Journal of the American Chemical Society, 126(9), 2885-2893; 2004. S-dealkylation/Reduction. Akao, Atsushi et al From Tetrahedron Letters, 47(30), 5337-5340; 2006. Cabiddu, S. et al From Synthesis, (7), 583-4; 1982.
Example 7




A polymer according to the present teachings that includes an M1 unit consists of only a moiety of formula (III) or (IV) and an M2 unit consists of only a pi-2 moiety can be prepared as described in Scheme 8 above.
Example 8
In embodiments where M1 has the formula:




where more specifically, m and m′ are 1 and each Ar is a substituted thienyl group, the dibromo-monomer below





can be prepared then used in a subsequent polymerization step, e.g., to copolymerize with a repeating unit pi-2 as shown in Scheme 9 below, where R3 is a dodecyl group.





Example 9
Molecular orbital (MO) calculations (B3LYP/6-31G*) (Spartan '08 Wavefunction, Inc. Irvine, Calif.) were carried out to compare vis-à-vis the geometrical parameters, electronic structure, and HOMO/LUMO energy levels of naphtho[1,2-d:5,6-d]bis[1,2,3]thiadiazole and naphtho[2,1-d:6,5-d]bis[1,2,3]thiadiazole versus those of the known parent system (naphtho[1,2-c:5,6-c]bis[1,2,5]thiadiazole). Both the unsubstituted cores and the 3,7-dithienyl substituted systems were calculated. These data demonstrate that all cores are very planar, which is essential for good charge transport for the corresponding molecular and polymeric semiconductors. Interestingly, the results show that while the MO topologies for both the HOMO and LUMO of the unsubstituted systems are considerably different, those of the thienyl-substituted have a similar pattern, although with different atomic contributions. This translates into a slight widening of the bandgap for the new systems, which exhibit deeper HOMO energies. This result is important for achieving semiconductors which may be more air stable (less sensitive to oxidation by air) in organic field-effect transistors and have greater open circuit voltage in organic photovoltaic devices.
The present teachings encompass embodiments in other specific forms without departing from the spirit or essential characteristics thereof. The foregoing embodiments are therefore to be considered in all respects illustrative rather than limiting on the present teachings described herein. Scope of the present invention is thus indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.

## Claims

1. A polymer comprising a repeating unit M1, wherein the repeating unit M1 comprises a moiety of the formula:



wherein:
X is a chalcogen;
R1, at each occurrence, independently is selected from the group consisting of H, halogen, —CN, NO2, R2, -L-R3, OH, OR2, OR3, NH2, NHR2, N(R2)2, NHR3, NR2R3, N(R3)2, SH, SR2, SR3, S(O)2OH, —S(O)2OR2, —S(O)2OR3, C(O)H, C(O)R2, C(O)R3, C(O)OH, C(O)OR2, C(O)OR3, C(O)NH2, C(O)NHR2, C(O)N(R2)2, C(O)NHR3, C(O)NR2R3, C(O)N(R3)2, SiH3, SiH(R2)2, SiH2(R2), and Si(R2)3, wherein L is selected from the group consisting of a divalent C1-40 alkyl group, a divalent C2-40 alkenyl group, a divalent C1-40 haloalkyl group, and a covalent bond; R2 is selected from the group consisting of a C1-40 alkyl group, a C2-40 alkenyl group, a C2-40 alkynyl group, and a C1-40 haloalkyl group; and R3 is selected from the group consisting of a C3-10 cycloalkyl group, a C6-14 aryl group, a C6-14 haloaryl group, a 3-12 membered cycloheteroalkyl group, and a 5-14 membered heteroaryl group, each of which optionally is substituted with 1-5 substituents selected from the group consisting of a halogen, —CN, NO2, R2, OR2, and SR2; and
the polymer has a degree of polymerization (n) ranging from 3 to 1,000.

2. The polymer of claim 1, wherein the chalcogen is sulfur.

3. The polymer of claim 1, wherein the repeating unit M1 has a formula selected from the group consisting of:



wherein:
pi-2 is an optionally substituted conjugated polycyclic moiety;
Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;
Z is a conjugated noncyclic linker;
m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0; and
p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

4. The polymer of claim 3, wherein R1, at each occurrence, independently is selected from the group consisting of H, F, Cl, —CN, —NO2, R2, OR2, and SR2, wherein R2 is selected from the group consisting of a linear or branched C1-40 alkyl group, a linear or branched C2-40 alkenyl group, and a linear or branched C1-40 haloalkyl group.

5. The polymer of claim 4 further comprising one or more repeating units other than M1, the one or more other repeating units (M2) being selected from the group consisting of:



wherein:
pi-2 is an optionally substituted conjugated polycyclic moiety;
Ar, at each occurrence, is independently an optionally substituted 5- or 6-membered aryl or heteroaryl group;
Z is a conjugated noncyclic linker;
m and m′ independently are 0, 1, 2, 3, 4, 5 or 6, provided that at least one of m and m′ is not 0;
m′′ is 1, 2, 3, 4, 5 or 6; and
p and p′ independently are 0 and 1, provided that at least one of p and p′ is 1.

6. The polymer of claim 5, wherein pi-2 is an optionally substituted C8-26 aryl group or 8-26 membered heteroaryl group.

7. The polymer of claim 6, wherein pi-2 is selected from the group consisting of:





















wherein:
Ra is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, and —C(O)OR;
Rb is selected from the group consisting of H, R, and -L′-Rf;
Rc is H or R;
Rd is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and -L′-Rf;
Re is selected from the group consisting of H, F, Cl, —CN, R, —OR, —SR, —C(O)R, —OC(O)R, —C(O)OR, and Rf;
Rf is a C6-20 aryl group or a 5-20-membered heteroaryl group, each optionally substituted with 1-8 groups independently selected from the group consisting of F, Cl, —CN, R, —OR, and —SR;
L′ is selected from the group consisting of —O—, —S—, —C(O)—, —OC(O)—, —C(O)O—, and a covalent bond; and
R is selected from the group consisting of a C1-40 alkyl group, a C1-40 haloalkyl group, a C2-40 alkenyl group, and a C2-40 alkynyl group.

8. The polymer of claim 5, wherein Ar in (Ar)m, (Ar)m′, and (Ar)m′′ is represented by:



wherein each W independently is selected from the group consisting of N, CH, and CR4, wherein R4 is selected from the group consisting of F, Cl, —CN, R2, OR2, SR2, C(O)R2, OC(O)R2, and C(O)OR2, and wherein R2 is selected from the group consisting of a C1-40 alkyl group, a C2-40 alkenyl group, a C2-40 alkynyl group, and a C1-40 haloalkyl group.

9. The polymer of claim 8, wherein (Ar)m, (Ar)m′, and (Ar)m′′ independently are selected from the group consisting of:

10. The polymer of claim 5, wherein Z is selected from:



wherein R4 is selected from F, Cl, —CN, R2, OR2, SR2, C(O)R2, OC(O)R2, and C(O)OR2, and wherein R2 is selected from a C1-40 alkyl group, a C2-40 alkenyl group, a C2-40 alkynyl group, and a C1-40 haloalkyl group.

11. The polymer of claim 5 represented by the formula:



wherein n is an integer ranging from 3 to 1,000.

12. The polymer of claim 1 having the formula:

13. The polymer of claim 1 having the formula:

14. The polymer of claim 1 having the formula:

15. An electronic device, an optical device, or an optoelectronic device comprising a thin film semiconductor component, the thin film semiconductor component comprising one or more polymers of claim 1.

16. The device of claim 12 configured as a thin film transistor, the thin film transistor comprising a substrate, a gate electrode, a gate dielectric component in contact with one side of the thin film semiconductor component, and source and drain electrodes in contact with an opposite side of the thin film semiconductor component.

17. The device of claim 12 configured as a photovoltaic device, the photovoltaic device comprising an anode, a cathode, optionally one or more anode interlayers, and optionally one or more cathode interlayers, wherein the thin film semiconductor component is disposed between the anode and the cathode.

18. The device of claim 12 configured as a light-emitting device, wherein the thin film semiconductor component comprising one or more polymers of claim 1 is photoactive.