WO2018021970A1

WO2018021970A1 - Conjugated polyviologen derivatives

Info

Publication number: WO2018021970A1
Application number: PCT/SG2017/050378
Authority: WO
Inventors: Teck Lip Dexter Tam; Aung Ko Ko Kyaw; Jishan WU
Original assignee: Agency For Science, Technology And Research
Priority date: 2016-07-25
Filing date: 2017-07-25
Publication date: 2018-02-01

Abstract

The present invention relates to an acceptor-acceptor type conjugated polymer that is an n-type conducting polymer having the following Formula (I): wherein Q is a bond, an optionally substituted aryl or an optionally substituted heteroaryl; A1 and A2 are independently hydrogen, halogen or an optionally substituted alkyl, or any two A1 may optionally be taken together to form an optionally substituted aryl; Ar is an optionally substituted electron deficient aryl that is N-conjugated directly to the pyridyl group; Y is a counterion; and n is an integer ranging from 5 to 100. The polymer of Formula (I) has a low LUMO value, and a high electron conductivity and air or oxygen stability. The present invention also relates to a method of synthesizing said polymer, and the use of said polymer. In a preferred embodiment, 2,6-dibromo-N,N'-bis(2-ethylhexyl)-1,8:4,5- naphthalene tetracarboxdiimide was reacted with 4,4'-bipyridine to form a conjugated polyviologen derivative in which the viologen unit covalently linked directly to an aromatic electron acceptor via the nitrogen atoms.

Description

Title of Invention: Conjugated Polyviologen derivatives

Technical Field

The present invention generally relates to a polymer that is a n-type conducting polymer that has high electron conductivity and is air-stable. The present invention also relates to a method of synthesizing said polymer, and the use of said polymer.

Background Art

Conducting polymers have been explored and used as interlayer charge transport materials in p-n junction devices, as well as electrode materials for better device operation. Conducting polymers are excellent candidates due to them being lightweight, flexible, low cost, and easy to handle for large scale deposition.

In almost all p-n junction devices, there is a need of both hole-transporting layer (HTL) and electron-transporting layer (ETL) for better device operation. Hole-transporting (p-type) conducting polymers such as poly (3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), polypyrrole (PPy) and polyaniline (PANI) are well established and have seen much success in device implementation. Electron-transporting (n-type) conducting polymers are also known, but none of the known n-type conducting polymers have high electron conductivity and/or are air-stable.

Based on electrochemical reduction potential, it has been deduced that the lowest unoccupied molecular orbital (LUMO) of n-type conducting polymers have to be lower than -4.9 eV in order to be stable against both oxygen and air. Taking into consideration a moderate overpotential of 0.5 V for oxygen reduction, it means that the LUMO of an n-type conducting polymer will need to be lower than -4.4 eV in order to be air stable. Achieving a LUMO of -4.4 eV and below is synthetically challenging in organic chemistry, and due to this, to-date, no air stable n-type conducting polymer has been reported.

There is therefore a need to provide a polymer and a method for preparing such a polymer that overcomes, or at least partially ameliorates one of more of the disadvantages described above.

Sum mary

In an aspect, there is provided a polymer having repeating units of the following Formula (I);

wherein Q is a bond or an optionally substituted aryl,

A¹ and A² are independently hydrogen or an optionally substituted alkyl, or any two A¹ may optionally be taken together to form an optionally substituted aryl;

Ar may be an optionally substituted electron deficient aryl that is N-conjugated directly to the pyridyl group,

Y may be a counterion, and n may be an integer ranging from 5 to 100.

In order to achieve a low lowest unoccupied molecular orbital (LUMO), careful and novel design of the polymer has to be considered. Advantageously, it was found that acceptor-acceptor type conjugated polymers based on N-conjugated polyviologen may achieve very low LUMO values. The air-stable n-type conducting polymer disclosed herein may advantageously consist of conjugated polyviologen in which the viologen unit may be covalently linked directly to an aromatic electron acceptor unit via the nitrogen atoms.

Advantageously, the polymer may be an n-type conducing polymer having a high electron conductivity of approximately 0.028 S cm^"1. More advantageously, the polymer may be air-stable. Further advantageously, the polymer may have a LUMO as low as -4.56 eV. More advantageously, the polymer may be highly soluble in a wide range of organic solvents, rendering the polymers solution processable. Further advantageously, the polymers may facilitate orthogonal solvent processing. Further advantageously, the polymer may be self-doped. That is, an additional dopant may not be needed to achieve high conductivity.

In another aspect, there is provided a method for synthesizing a polymer having repeating units of the following formula (V),

wherein Q is a bond or an optionally substituted aryl,

Ar may be an optionally substituted electron deficient aryl that is N-conjugated directly to the 4,4'-bipyridyl group and n is an integer ranging from 5 to 100; the method may comprise the step of contacting a compound having the following Formula (Ilia):

with a compound having the following Formula (Illb):

X-Ar-X (Illb), wherein X may be a leaving group; under reaction conditions.

The synthesis of such N-conjugated polyviologens may involve simple nucleophilic aromatic substitution between an electron deficient aromatic group with two good leaving groups X and 4,4'- bipyridine.

In an embodiment, there is provided the method as defined above, further comprising the step of performing anion exchange to obtain a polymer having repeating units of the following Formula (I):

wherein Y may be selected from the group consisting of CI, Br, I, F, hydroxide, tosylate, gluconate, lactate, acetate, formate, pyruvate, galacturonate, nitrile, trifluoroacetate, nitrate, glutarate, succinate, carbonate, tartrate, benzoate, maleate, sulfate, fumarate, sulfonate, p-toluenesulfonate, methanesulfonate, benzensulfonate, phosphate, citrate, tetrafluoroborate, hexafluorophosphate, bis(trifluoromethane)sulfonimide, hexafluoroantimonate and any mixtures thereof.

Advantageously, higher conductivity may be achieved depending on the counteranion used. In another aspect, there is provided the use of a polymer as defined above as a conducting polymer.

Advantageously, due to the high electron conductivity and air-stability, the polymer may be useful in any p-n junction, hybrid thermoelectrics and polymer cathode for batteries or supercapacitors.

Definitions

In this specification a number of terms are used which are well known to a skilled addressee. Nevertheless for the purposes of clarity a number of terms will be defined. The following words and terms used herein shall have the meaning indicated:

In the definitions of a number of substituents below it is stated that "the group may be a terminal group or a bridging group". This is intended to signify that the use of the term is intended to encompass the situation where the group is a linker between two other portions of the molecule as well as where it is a terminal moiety. Using the term alkyl as an example, some publications would use the term "alkylene" for a bridging group and hence in these other publications there is a distinction between the terms "alkyl" (terminal group) and "alkylene" (bridging group). In the present application no such distinction is made and most groups may be either a bridging group or a terminal group.

"Acyl" means an R-C(=0)- group in which the R group may be an alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl group as defined herein. Examples of acyl include acetyl and benzoyl. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the carbonyl carbon.

"Alkenyl" as a group or part of a group denotes an aliphatic hydrocarbon group containing at least one carbon-carbon double bond and which may be straight or branched preferably having 2-12 carbon atoms, more preferably 2-10 carbon atoms, most preferably 2-6 carbon atoms, in the normal chain. The group may contain a plurality of double bonds in the normal chain and the orientation about each is independently E or Z. Exemplary alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and nonenyl. The group may be a terminal group or a bridging group.

"Alkyl" as a group or part of a group refers to a straight or branched aliphatic hydrocarbon group, preferably a C₁-C25 alkyl, more preferably a C₁-C₁₀ alkyl, most preferably Ci-C₆ unless otherwise noted. Examples of suitable straight and branched Ci-C₆ alkyl substituents include methyl, ethyl, n- propyl, 2-propyl, n-butyl, sec-butyl, t-butyl, hexyl, and the like. The group may be a terminal group or a bridging group.

"Alkylamino" includes both mono-alkylamino and dialkylamino, unless specified. "Mono- alkylamino" means a Alkyl-NH- group, in which alkyl is as defined herein. "Dialkylamino" means a (alkyl)₂N- group, in which each alkyl may be the same or different and are each as defined herein for alkyl. The alkyl group is preferably a Ci-C₆ alkyl group. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom. "Alkyloxy" refers to an alkyl-O- group in which alkyl is as defined herein. Preferably the alkyloxy is a Ci-C₆alkyloxy. Examples include, but are not limited to, methoxy and ethoxy. The group may be a terminal group or a bridging group.

"Alkynyl" as a group or part of a group means an aliphatic hydrocarbon group containing a carbon- carbon triple bond and which may be straight or branched preferably having from 2-12 carbon atoms, more preferably 2-10 carbon atoms, more preferably 2-6 carbon atoms in the normal chain. Exemplary structures include, but are not limited to, ethynyl and propynyl. The group may be a terminal group or a bridging group.

"Amino" refers to groups of the form -NR_aR_¾ wherein R_a and R_¾ are individually selected from the group including but not limited to hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, and optionally substituted aryl groups.

"Aryl" as a group or part of a group denotes (i) an optionally substituted monocyclic, or fused polycyclic, aromatic carbocycle (ring structure having ring atoms that are all carbon) preferably having from 5 to 18 atoms per ring. Examples of aryl groups include phenyl, naphthyl, and the like; (ii) an optionally substituted partially saturated bicyclic aromatic carbocyclic moiety in which a phenyl and a C₅_₇ cycloalkyl or C₅_₇ cycloalkenyl group are fused together to form a cyclic structure, such as tetrahydronaphthyl, indenyl or indanyl. The group may be a terminal group or a bridging group. Typically an aryl group is a C₃-Ci₈ aryl group.

A "bond" is a linkage between atoms in a compound or molecule. The bond may be a single bond, a double bond, or a triple bond.

"Cycloalkenyl" means a non-aromatic monocyclic or multicyclic ring system containing at least one carbon-carbon double bond and preferably having from 5-10 carbon atoms per ring. Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl or cycloheptenyl. The cycloalkenyl group may be substituted by one or more substituent groups. A cycloalkenyl group typically is a C₃-Ci₂ alkenyl group. The group may be a terminal group or a bridging group.

"Cycloalkyl" refers to a saturated monocyclic or fused or spiro polycyclic, carbocycle preferably containing from 3 to 9 carbons per ring, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, unless otherwise specified. It includes monocyclic systems such as cyclopropyl and cyclohexyl, bicyclic systems such as decalin, and polycyclic systems such as adamantane. A cycloalkyl group typically is a C₃-Ci₂ alkyl group. The group may be a terminal group or a bridging group.

"Halogen" represents chlorine, fluorine, bromine or iodine.

"Cycloamino" refers to a saturated monocyclic, bicyclic, or polycyclic ring containing at least one nitrogen in at least one ring. Each ring is preferably from 3 to 10 membered, more preferably 4 to 7 membered. The group may be a terminal group or a bridging group. If the group is a terminal group it is bonded to the remainder of the molecule through the nitrogen atom. "Haloalkyl" refers to an alkyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine. A haloalkyl group typically has the formula C_nH₍₂n₊i-m)Xm wherein each X is independently selected from the group consisting of F, CI, Br and I . In groups of this type n is typically from 1 to 10, more preferably from 1 to 6, most preferably 1 to 3. m is typically 1 to 6, more preferably 1 to 3. Examples of haloalkyl include fluoromethyl, difluoromethyl and trifluoromethyl.

"Haloalkenyl" refers to an alkenyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom independently selected from the group consisting of F, CI, Br and I.

"Haloalkynyl" refers to an alkynyl group as defined herein in which one or more of the hydrogen atoms has been replaced with a halogen atom independently selected from the group consisting of F, CI, Br and I.

"Heteroalkyl" refers to a straight- or branched-chain alkyl group preferably having from 2 to 12 carbons, more preferably 2 to 6 carbons in the chain, one or more of which has been replaced by a heteroatom selected from S, O, P and N. Exemplary heteroalkyls include alkyl ethers, secondary and tertiary alkyl amines, amides, alkyl sulfides, and the like. Examples of heteroalkyl also include hydroxyCi-C₆alkyl, Ci-C₆alkyloxyCi-C₆alkyl, aminoCi-C₆alkyl, Ci-C₆alkylaminoCi-C₆alkyl, and di(Ci-C₆alkyl)aminoCi-C₆alkyl. The group may be a terminal group or a bridging group.

"Heteroaryl" either alone or part of a group refers to groups containing an aromatic ring (preferably a 5 or 6 membered aromatic ring) having one or more heteroatoms as ring atoms in the aromatic ring with the remainder of the ring atoms being carbon atoms. Suitable heteroatoms include nitrogen, oxygen and sulphur. Examples of heteroaryl include thiophene, benzothiophene, benzofuran, benzimidazole, benzoxazole, benzothiazole, benzisothiazole, naphtho[2,3-b]thiophene, furan, isoindolizine, xantholene, phenoxatine, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, tetrazole, indole, isoindole, lH-indazole, purine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, cinnoline, carbazole, phenanthridine, acridine, phenazine, thiazole, isothiazole, phenothiazine, oxazole, isooxazole, furazane, phenoxazine, 2-, 3- or 4- pyridyl, 2-, 3-, 4-, 5-, or 8- quinolyl, 1-, 3-, 4-, or 5- isoquinolinyl 1-, 2-, or 3- indolyl, and 2-, or 3-thienyl. A heteroaryl group is typically a Ci-Cig heteroaryl group. The group may be a terminal group or a bridging group. Typically a heteroaryl group is a 3 to 18 membered group.

"Heterocyclic" refers to saturated, partially unsaturated or fully unsaturated monocyclic, bicyclic or polycyclic ring system containing at least one heteroatom selected from the group consisting of nitrogen, sulfur and oxygen as a ring atom. Examples of heterocyclic moieties include heterocycloalkyl, heterocycloalkenyl and heteroaryl.

"Lower alkyl" as a group means unless otherwise specified, an aliphatic hydrocarbon group which may be straight or branched having 1 to 6 carbon atoms in the chain, more preferably 1 to 4 carbons such as methyl, ethyl, propyl (n-propyl or isopropyl) or butyl (n-butyl, isobutyl or tertiary-butyl). The group may be a terminal group or a bridging group. The term "optionally substituted" as used herein means the group to which this term refers may be unsubstituted, or may be substituted with one or more groups independently selected from alkyl, alkenyl, alkynyl, thioalkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, cycloalkylalkenyl, heterocycloalkyl, cycloalkylheteroalkyl, cycloalkyloxy, cycloalkenyloxy, cycloamino, halo, carboxyl, haloalkyl, haloalkynyl, alkynyloxy, heteroalkyl, heteroalkyloxy, hydroxyl, hydroxyalkyl, alkoxy, thioalkoxy, alkenyloxy, haloalkoxy, haloalkenyl, haloalkynyl, haloalkenyloxy, nitro, amino, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroheterocyclyl, alkylamino, dialkylamino, alkenylamine, aminoalkyl, alkynylamino, acyl, alkyloxy, alkyloxyalkyl, alkyloxyaryl, alkyloxycarbonyl, alkyloxycycloalkyl, alkyloxyheteroaryl, alkyloxyheterocycloalkyl, alkenoyl, alkynoyl, acylamino, diacylamino, acyloxy, alkylsulfonyloxy, heterocyclic, heterocycloalkenyl, heterocycloalkyl, heterocycloalkylalkyl, heterocycloalkylalkenyl, heterocycloalkylheteroalkyl, heterocycloalkyloxy, heterocycloalkenyloxy, heterocycloxy, heterocycloamino, haloheterocycloalkyl, alkylsulfinyl, alkylsulfonyl, alkylsulfenyl, alkylcarbonyloxy, alkylthio, acylthio, aminosulfonyl, phosphorus- containing groups such as phosphono and phosphinyl, sulfinyl, sulfinylamino, sulfonyl, sulfonylamino, aryl, heteroaryl, heteroarylalkyl, heteroarylalkenyl, heteroarylheteroalkyl, heteroarylamino, heteroaryloxy, arylalkenyl, arylalkyl, alkylaryl, alkylheteroaryl, aryloxy, arylsulfonyl, cyano, cyanate, isocyanate, -C(0)NH(alkyl), and -C(0)N(alkyl)₂.

"Viologen" as used herein refers to compounds comprising 4,4'-bipyridyl comprising quaternary nitrogens. The term "viologen", for the purposes of this disclosure, may also encompass extended viologens whereby an aromatic group is present between the two pyridinium moieties, whereby the aromatic group is covalently bound to the pyridinium moieties but not N-conjugated. The term "polyviologen" should be construed accordingly to refer to repeating units of viologens.

Some of the compounds of the disclosed embodiments may exist as single stereoisomers, racemates, and/or mixtures of enantiomers and /or diastereomers. All such single stereoisomers, racemates and mixtures thereof, are intended to be within the scope of the subject matter described and claimed.

The word "substantially" does not exclude "completely" e.g. a composition which is "substantially free" from Y may be completely free from Y. Where necessary, the word "substantially" may be omitted from the definition of the invention.

Unless specified otherwise, the terms "comprising" and "comprise", and grammatical variants thereof, are intended to represent "open" or "inclusive" language such that they include recited elements but also permit inclusion of additional, unrecited elements.

As used herein, the term "about", in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.

Throughout this disclosure, certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub- ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

Certain embodiments may also be described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the disclosure. This includes the generic description of the embodiments with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.

Brief Description of Drawings

The accompanying drawings illustrate a disclosed embodiment and serves to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.

Fig. 1

[Fig. 1] is a schematic diagram showing how the inventive polymer is prepared. Fig. 2

[Fig. 2] is the ¾ NMR spectrum of Polymer 1 (pNDIBPy.Br). Fig. 3

[Fig. 3] is the ¾ NMR spectrum of Polymer 2 (pNDIBPy.I). Fig. 4

[Fig. 4] is the UV-Vis-NIR spectrum of Polymers 1 and 2. Fig. 5

[Fig. 5] is a graph showing the sheet resistance of Polymer 1 over 14 days. Fig. 6

[Fig. 6] is a diagram showing the electron conductivity of the inventive polymers compared to pre-existing compounds

Fig. 7

[Fig. 7] is a graph showing the cyclic voltammetry of Polymer 1. Fig. 8

[Fig. 8] is a schematic representation showing the LUMO of Polymer 1.

Fig. 9

[Fig. 9] refers to graphs of current density and luminance against voltage of a quantum dot light- emitting diode (LED) in an inverted structure when ZnO (control, Fig. 9A) and pNDIBPy.I. (Fig. 9B) is used as the electron transport layer (ETL).

Detailed Description of Embodiments

There is provided a polymer having repeating units of the following Formula (I);

Q may be a bond, an optionally substituted aryl or an optionally substituted heteroaryl. Q may be an optionally substituted poly cyclic aryl or an optionally substituted poly cyclic heteroaryl. Q may be an aryl selected from the group consisting of:

attaches to the pyridinium groups.

A¹ and A² may independently be hydrogen, halogen or an optionally substituted alkyl, or any two A¹ may optionally be taken together to form an optionally substituted aryl. A¹ and A² may independently be hydrogen or fluorine.

The polymer may have repeating units of the following Formula (la):

The polymer may have repeating units of the following Formula (lb), (Ic) or (Id):

Ar may be an optionally substituted electron deficient aryl that is N-conjugated directly to the pyridyl group.

Ar may be N-conjugated directly to the pyridyl group without any linkers.

The structure of Ar may comprise a group selected from the group consisting of aryl imide, aryl diimide, aryl diketone and aryl tetraketone.

The structure of Ar may comprise a group selected from the group consisting of Formula (Ha), (lib), (lie) and (lid):

Formula (Ha), (lib), (lie) and (lid) may be optionally substituted.

R¹ may be optionally substituted alkyl. R¹ may be a Ci to C₂₀ alkyl. R¹ may be Ci to C₅ alkyl, Ci to Cio alkyl, Ci to Ci₅ alkyl, C₅ to Cio alkyl, C₅ to Ci₅ alkyl, C₅ to C₂₀ alkyl, Cio to Ci₅ alkyl, Cio to C₂₀ alkyl or Ci₅ to C₂o alkyl.

R¹ may be linear or branched.

R¹ may have the following formula (IV):

h may be 0 or 1. i and j may independently be integers selected from 1 to 18, 1 to 3, 1 to 6, 1 to 9, 1 to 12, 1 to 15, 3 to 6, 3 to 9, 3 to 12, 3 to 15, 3 to 18, 6 to 9, 6 to 12, 6 to 15, 6 to 18, 9 to 12, 9 to 15, 9 to 18, 12 to 15, 12 to 18 or 15 to 18. i and j may independently be an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18.

The bond broken

may be where the R¹ is attached to Formula (Ila) or (lib), h may be 1, i may be 2 and j may be 4.

R¹ may be selected from the group consisting of methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl,l-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, 1-hexyl, 2- methylpentyl, 3-methylpentyl, 2,2-dimetlybutyl, 2,3-dimethylbutyl, 1-heptyl, 2-methylheptyl, 3- methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3- ethylpentyl, 2,2,3-trimethylbutyl, 1-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2- dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3,4- dimethylhexyl, 3-ethylhexyl, 2,2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 2,3,4-trimethylpentyl, 2-methyl-3-ethylpentyl, 3-methyl-3-ethylpentyl, tetramethylbutyl, 2-ethyl-l- hexyl, 2-butyl- 1-octyl, 2-hexyl-l-decyl and 2-octyl-l-dodecyl.

Z may be O or S. Z may be O. — may be a single bond or where the compound of Formulae (Ila), (lib), (lie) or (lid) is fused to the rest of Ar.

When— is a single bond, Formulae (Ila), (lib), (lie) and (lid) may have the following Formula (Ila'), (lib'), (lie') or (lid'):

(Ila') (lib') (lie') (lid')

Formula (Ila'), (lib'), (He') and (lid') may be optionally substituted.

The group of Formula (Ila), (lib), (lie) or (lid) may be independently optionally fused to at least one optionally substituted aryl. The optionally substituted aryl may be selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, naphthalene, triphenylene, chrysene, pyrene, corannulene, coronene, perylene, hexahelicene, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, quinazoline, pyridazine, and cinnoline. The optionally substituted aryl may be benzene, naphthalene or perylene.

Ar or the electron deficient aryl may be selected from the group consisting of:

where the R¹ is attached to Formula (Ila) or (lib).

Ar or the electron deficient aryl may be optionally substituted.

R¹ and R² may be independently optionally substituted alkyl, and the bond broken

may be where the Ar is N-conjugated directly to the 4,4 '-bipyridyl group.

R¹ and R² may both be an optionally substituted alkyl.

R¹ and R² may independently be Ci to C₂₀ alkyl, Ci to C₅ alkyl, Ci to Cio alkyl, Ci to Ci₅ alkyl, C₅ to Cio alkyl, C₅ to Ci₅ alkyl, C₅ to C₂₀ alkyl, Cio to Ci₅ alkyl, Cio to C₂₀ alkyl or Ci₅ to C₂o alkyl. R¹ and R² may independently be linear or branched.

R¹ and R² may independently have the following formula (IV):

h may be 0 or 1. i and j may independently be integers selected from 1 to 18, 1 to 3, 1 to 6, 1 to 9, 1 to 12, 1 to 15, 3 to 6, 3 to 9, 3 to 12, 3 to 15, 3 to 18, 6 to 9, 6 to 12, 6 to 15, 6 to 18, 9 to 12, 9 to 15, 9 to 18, 12 to 15, 12 to 18 or 15 to 18. i and j may independently be an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18. h may be 1, i may be 2 and j may be 4.

R¹ and R² may be independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. R¹ and R² may independently be selected from the group consisting of methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl,l -pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, 1-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimetlybutyl, 2,3- dimethylbutyl, 1-heptyl, 2-methylheptyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4- dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, 1-octyl, 2-methylheptyl, 3- methylheptyl, 4-methylheptyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5- dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3-ethylhexyl, 2,2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 2,3,4-trimethylpentyl, 2-methyl-3-ethylpentyl, 3- methyl-3-ethylpentyl, tetramethylbutyl, 2 -ethyl- 1-hexyl, 2-butyl- 1-octyl, 2-hexyl-l-decyl and 2- octyl-l-dodecyl.

Y may be a counterion. Y may be selected from the group consisting of CI, Br, I, F, hydroxide, tosylate, gluconate, lactate, acetate, formate, pyruvate, galacturonate, nitrile, trifluoroacetate, nitrate, glutarate, succinate, carbonate, tartrate, benzoate, maleate, sulfate, fumarate, sulfonate, p- toluene sulfonate, methane sulfonate, benzensulfonate, phosphate, citrate, tetrafluoroborate, hexafluorophosphate, bis(trifluoromethane)sulfonimide, hexafluoroantimonate and any mixtures thereof. Y may be Br, I or hydroxide. n may be an integer ranging from 5 to 100. n may be an integer ranging from 10 to 50. n may be an integer ranging from 12 to 25.

The polymer may have the following structures:

The polymer may be soluble in an organic solvent. The organic solvent may be selected from the group consisting of acetonitrile, N,N-Dimethylmethanamide, dimethyl sulfoxide, N-methyl-2- pyrrolidone, and dimethylacetamide.

There is provided a method for synthesizing a polymer having repeating units of the following formula (V),

Q may be a bond, an optionally substituted aryl, or an optionally substituted heteroaryl. Q may be an optionally substituted poly cyclic aryl or an optionally substituted poly cyclic heteroaryl. Q may be an aryl selected from the group consisting of:

attaches to the pyridinium groups.

Ar may be an optionally substituted electron deficient aryl that is N-conjugated directly to the pyridyl group as defined above, and n may be an integer ranging from 5 to 100.

The method may comprise the step of contacting a compound having the following Formula (Ilia):

with a compound having the following Formula (Mb):

X-Ar-X (Illb), wherein X ma}⁷ be a leaving group; under reaction conditions.

The method may comprise the step of N-conjugating the Ar directly to the 4pyridyl group without any linkers.

The polymer may be selected to have repeating units of the following formula (Va):

The polymer may be selected to have repeating units of the following Formula (Vb), (Vc) or (Vd):

(Vc)

The structure of Ar may be selected to comprise a group selected from the group consisting of aryl imide, aryl diimide, aryl diketone and aryl tetraketone.

The structure of Ar may be selected to comprises a group selected from the group consisting Formula (Ila), (lib), (lie) and (lid):

Formula (Ila), (lib), (lie) and (lid) may be optionally substituted.

R¹ may be optionally substituted alkyl. R¹ may be a Ci to C₂₀ alkyl. R¹ may be Ci to C₅ alkyl, Ci to Cio alkyl, Ci to Ci₅ alkyl, C₅ to Ci₀ alkyl, C₅ to Ci₅ alkyl, C₅ to C₂₀ alkyl, Ci₀ to Ci₅ alkyl, Ci₀ to C₂₀ alkyl or Ci₅ to C₂o alkyl.

R¹ may be linear or branched.

R¹ may have the following formula (IV):

The bond broken

may be where the R¹ is attached to Formula (Ila) or (lib). h may be 1, i may be 2 and j may be 4.

R¹ may be selected from the group consisting of methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl, l-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, 1-hexyl, 2- methylpentyl, 3-methylpentyl, 2,2-dimetlybutyl, 2,3-dimethylbutyl, 1-heptyl, 2-methylheptyl, 3- methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3- ethylpentyl, 2,2,3-trimethylbutyl, 1-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,2- dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 3,3-dimethylhexyl, 3,4- dimethylhexyl, 3-ethylhexyl, 2,2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 2,3,3-trimethylpentyl, 2,3,4-trimethylpentyl, 2-methyl-3-ethylpentyl, 3-methyl-3-ethylpentyl, and tetramethylbutyl, , 2-ethyl- 1-hexyl, 2-butyl- 1-octyl, 2-hexyl-l -decyl and 2-octyl-l -dodecyl.

Z may be O or S. Z may be O.

— may be a single bond or where the compound of Formulae (Ila), (lib), (lie) or (lid) is fused to the rest of Ar.

Formula (Ila'), (lib'), (He') and (lid') may be optionally substituted.

The group of Formula (Ila), (lib), (lie) or (lid) may be selected to be independently optionally fused to at least one optionally substituted aryl. The optionally substituted aryl may be selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, naphthalene, triphenylene, chrysene, pyrene, corannulene, coronene, perylene, hexahelicene, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, quinazoline, pyridazine, and cinnoline. The optionally substituted aryl may be benzene, naphthalene or perylene. the electron deficient aryl may be selected from the group consisting of:

where the R¹ is attached to Formula (Ila) or (lib). Ar or the electron deficient aryl may be optionally substituted.

R¹ and R² may be independently optionally substituted alkyl, and the bond broken by»/vw is where the Ar is N-conjugated directly to the 4,4'-bipyridyl group.

R¹ and R² may both be an optionally substituted alkyl.

R¹ and R² may independently be Ci to C₂₀ alkyl, Ci to C₅ alkyl, Ci to Cio alkyl, Ci to Ci₅ alkyl, C₅ to Cio alkyl, C₅ to Ci₅ alkyl, C₅ to C₂₀ alkyl, Cio to Ci₅ alkyl, Cio to C₂₀ alkyl or Ci₅ to C₂o alkyl.

R¹ and R² may independently be linear or branched.

R¹ and R² may independently have the following formula (IV):

R¹ and R² may be independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. R¹ and R² may independently be selected from the group consisting of methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl,l -pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, 1-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimetlybutyl, 2,3- dimethylbutyl, 1 -heptyl, 2-methylheptyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4- dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, 1-octyl, 2-methylheptyl, 3- methylheptyl, 4-methylheptyl, 2,2-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5- dimethylhexyl, 3,3-dimethylhexyl, 3,4-dimethylhexyl, 3-ethylhexyl, 2,2,3-trimethylpentyl, 2,2,4- trimethylpentyl, 2,3,3-trimethylpentyl, 2,3,4-trimethylpentyl, 2-methyl-3-ethylpentyl, 3-methyl-3- ethylpentyl, tetramethylbutyl, 2-ethyl- 1-hexyl, 2-butyl- 1-octyl, 2-hexyl-l-decyl and 2-octyl-l-dodecyl.

X may be selected to be a weak base. X may be selected from the group consisting of CI, Br, I, tosylate, sulfonate, p-toluenesulfonate, and methanesulfonate. X may be Br.

The compound of Formula (Ilia) may be 4,4'-bipyiridine. The compound of Formula (Ilia) may be selected from the following:

The compound of Formula (Illb) may selected from the following:

The compound of Formula (Illb) may be selected to have the following structure:

The step of contacting the compound of Formula (Ilia) and (Illb) may be performed at a temperature in the range of about 100 °C to about 170 °C, about 100 °C to about 120 °C, about 100 °C to about 140 °C, about 100 °C to about 160 °C, about 120 °C to about 140 °C, about 120 °C to about 160 °C, about 120 °C to about 170 °C, about 140 °C to about 160 °C, about 140 °C to about 170 °C, or about 160 °C to about 170 °C. The step of contacting the compound of Formula (Ilia) and (Illb) may be performed at a temperature of about 140 °C.

The step of contacting the compound of Formula (Ilia) and (Illb) may be performed for a duration of about 48 hours to about 96 hours, about 48 hours to about 72 hours, or about 72 hours to about 96 hours. The step of contacting the compound of Formula (Ilia) and (Illb) may be performed for a duration of about 72 hours.

The method may further comprise a purification step to remove solids having a molecular weight of less than about 3000, less than about 1500, less than about 1000 or less than about 500. The method may further comprise the step of performing anion exchange to obtain a polymer having repeating units of the following Formula (I):

Y may be selected from the group consisting of CI, Br, I, F, hydroxide, tosylate, gluconate, lactate, acetate, formate, pyruvate, galacturonate, nitrile, trifluoroacetate, nitrate, glutarate, succinate, carbonate, tartrate, benzoate, maleate, sulfate, fumarate, sulfonate, p-toluenesulfonate, methanesulfonate, benzensulfonate, phosphate, citrate, tetrafluoroborate, hexafluorophosphate, bis(trifluoromethane)sulfonimide, hexafluoroantimonate and any mixtures thereof. Y may be Br, I or hydroxide.

The method may further comprise the step of performing anion exchange to obtain a polymer having repeating units of the following Formula (la):

Electrical conductivity of conjugated polyviologens may arise from electron transfer from the counter anion to the polymer, resulting in the formation of polyradical species that may be viewed as the charge carriers. Electrical conductivity is proportional to the product of mobility and carrier concentration. By switching the counter anion that facilitates better electron transfer, it may be possible to increase the carrier concentration and thus electrical conductivity of the polymer. n may be an integer ranging from 5 to 100. n may be an integer ranging from 10 to 50. n may be an integer ranging from 12 to 25.

The method may provide a polymer having the following structures:

Examples

Non-limiting examples of the disclosure and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.

The synthetic steps are disclosed in a general manner in the following synthetic methods. Variations of these general methods in order to produce the polymers according to the present disclosure are within the ability of the person skilled in the art. Where representative procedures are given, these can be adjusted by the person skilled in the art to other derivatives, if needed.

EXAMPLE 1: Materials and Methods

Materialsand Methods

Br₂-NDI and 4,4'-bipyridiyl were obtained from Tokyo Chemical Industry Co. Ltd. (Japan) and used without further purification unless otherwise stated. Sodium iodide and the anhydrous solvents were obtained from Sigma Aldrich (USA) and used without further purification unless otherwise stated.

¾ and ¹ C NMR were performed on JEOL 500MHz NMR system with chemical shifts referenced to the deuterated solvent. Elemental analysis was carried out using CHNS FlashEA 1112 Elemental Analyzer from Thermo Fisher Scientific. UV-Vis-NIR absorption spectra were recorded on a Shimadzu UV-3101PC UV-VIS-NIR Spectrophotometer. Cyclic voltammetry (CV) experiments were performed using Autolab potentiostat (model PGSTAT30) by Echochimie. All CV measurements were recorded in dry acetonitrile with 0.1 M tetrabutylammonium hexafluorophosphate as supporting electrolyte (scan rate of 100 mV's^"1), glassy carbon disk as working electrode, gold disk as counter electrode and Ag/AgCl as reference electrode. Ferrocene was used as external standard. Continuous wave X-band ESR spectra were obtained with a JEOL (FA200) spectrometer at room temperature using dry solvents. XPS spectra were measured on powder samples using VG Thermo Escalab 220i - XL X-ray photoelectron spectroscopy system. XPS data is analyzed using Thermo Avantage v4.12. Gel Permeation Chromatography molecular weight analysis was measured using 0.1M LiBr in DMF as eluent.

Example2: Preparationof Polymer 1

Polymer 1 (pNDIBPy.Br.)

Polymer 1 was prepared as shown in Fig. 1. pNDIBPy.Br. 200 mg of 2,6-dibromo-N,N-bis(2-ethylhexyl)-l,8:4,5-naphthalene tetracarboxdiimide (Br₂-NDI, 0.31 mmol) and 48.2 mg of 4,4'-bipyridine (0.31 mmol) were added into an one-neck round-bottom flask. 4 mL of anhydrous dimethylacetamide was added and the reaction setup was purged with nitrogen. The reaction mixture was heated at 140 °C in a preheated oil bath for 72 hours. The reaction was allowed to cool to room temperature and precipitated in 200 mL of diethyl ether. The suspension was filtered and washed with diethyl ether. Soxhlet extraction was carried out to remove low molecular weight solids to yield the polymer. Yield 87%. Gel Permeation Chromatography in 0.1 M LiBr in DMF against polystyrene standards, M_w: 18674, Poly Dispersity Index: 1.67. The ^MR spectrum is shown in Fig. 2 and the UV-Vis-NIR spectrum is shown in Fig. 4.

E AMPLE 3: Preparation of Polymer 2

Polymer2 (pNDIBPy.I.)

Polymer 2 was prepared by as shown in Fig. 1. I₂-NDI. 500 mg of 2,6-dibromo-N,N-bis(2-ethylhexyl)-l,8:4,5-naphthalene tetracarboxdiimide (Br₂- NDI, 0.77 mmol), 4.623 g of Nal (30.84 mmol), 25 mL of THF and 25 mL of NMP were added into a two-necked round-bottom flask with a condenser attached. The reaction setup was purged with nitrogen and heated at 80 °C for 24 hours. The reaction was allowed to cool to room temperature and precipitated in 100 mL of methanol. The solids were filtered, washed with methanol and dried. TLC and NMR showed almost complete conversation of the dibromo starting material to the diiodo product with some monobromo monoiodo intermediate (— 5 — 10 %) present. Due to the poor solubility of the diiodo product, column chromatography was unable to purify the mixture. Instead, the reaction was repeated 2 - 3 times using the crude product to ensure complete conversion. The product was purified by dissolving in hot THF, cooled to room temperature and poured into ethanol. The yellow solids were filtered, washed with ethanol, followed by methanol and dried under vacuum. Yield: 475 mg (83 %). ¾ NMR (500 MHz, Chloroform- ) δ 9.33 (s, 2H), 4.40 - 3.91 (m, 4H), 1.94 (tt, J = 13.7, 6.7 Hz, 2H), 1.43 - 1.23 (m, 16H), 0.93 (t, J = 7.4 Hz, 6H), 0.88 (t, J = 1.1 Hz, 6H). ¹ C NMR (126 MHz, Chloroform- ) δ 161.30, 161.21, 145.73, 128.10, 126.95, 124.42, 100.50, 45.45, 37.88, 30.74, 28.66, 24.10, 23.23, 14.23, 10.72. Anal. Calcd for

C, 48.53; H, 4.89; I, 34.19; N, 3.77; O, 8.62. Found: C, 48.68; H, 4.91; N, 3.88. MALDI-TOF-MS m/z: 740.93 (M-H⁺); calcd. for C₃₀H₃₆I₂N₂O = 742.08. pNDIBPy.I. 114.5 mg of 2,6-diiodo-N,N-bis(2-ethylhexyl)-l,8:4,5-naphthalene tetracarboxdiimide (I₂-NDI, 0.16 mmol) and 24.1 mg of 4,4'-bipyridine (0.16 mmol) were added into an one-neck round- bottom flask. 2 mL of anhydrous dimethylacetamide was added and the reaction setup was purged with nitrogen. The reaction mixture was heated at 140 °C in a preheated oil bath for 72 hours. The reaction was allowed to cool to room temperature and precipitated in 100 mL of diethyl ether. The suspension was filtered and washed with diethyl ether. Soxhlet extraction was carried out to remove low molecular weight solids to yield the polymer. Yield: 98 mg (71 %). Gel Permeatiom Chromatodraphy in 0.1 M LiBr in DMF against polystyrene standards, M_w: 20824, Poly Dispersity Index: 1.06. ¾MR spectrum is shown in Fig. 3 an the UV-Vis-NIR spectrum is shown in Fig. 4.

EXAMPLE 4: Air Stability

The conjugated polyviologen thin film of polymer 1 having a thickness of approximately 70 nm gave sheet resistance of approximately 6 x 10⁶ Ω/sq when measured in air at 25 °C and 70 % humidity using a four-point probe resistivity set up. This converts to an electrical conductivity of 0.024 Scm^"1. The sheet resistance remained constant even over 2 weeks, as shown in Fig. 5, indicating that the polymer is air stable.

EXAMPLE 5: Conductivity

Further, the measured electron conductivity of the polymer was found to be higher than some of the commercial grade p-type conducting PEDOT:PSS. Using commercial grade PEDOT:PSS as a guideline, charge transport interlayer material normally has a conductivity in the range of 10^"6 to 1 Scm^"1 (Clevios™ POLED grades), and the electrode material normally has a conductivity of 1 to 1000 Scm^"1 (in situ polymerized PEDOT). The inventive polymer was found to have a conductivity in this range as indicated by the band 601 in Fig. 6. EXAMPLE 6: Cyclic Voltammetrv

The air-stability of polymer 1 and 2 is a result of a very low lowest unoccupied molecular orbital (LUMO) which was determined to be— 4.5 to -4.8 eV using solution cyclic voltammetry in acetonitrile (Fig. 7).

The cyclic voltammetry determined the highest occupied molecular orbital (HOMO) and LUMO, and this is supported by Density Functional Theory (DFT) calculations of the monomer using geometry optimization at B3LYP 6-31G d,p level of theory with acetonitrile as the solvent, as shown in Fig. 8. The HOMO localized on the atomic orbitals of bromine while the LUMO is located on the polymer backbone. Thus the electrical conductivity of the conjugated polyviologen arises from electron conductivity (n-type) but not hole conductivity (p-type).

The conductivity of the conjugated polyviologen is believed to arise from a halogen-induced doping effect which is similar to what has been reported in the past for tetrabutylammonium fluoride doped C60 and phenyl-C61 -butyric acid methyl ester (PCBM), as well as PCBM derivatives. However, in the previously known examples, the n-type conductivities of the resulting films were not air-stable. The inventive polymer has a significantly lower LUMO of approximately — 4.5 to -4.8 eV compared to the LUMO of PCBM and its derivatives of approximately -4.0 eV, and this low LUMO is believe to facilitate the air-stable n-type conductivity in the inventive polymer.

It is therefore suggested that by replacing the anion with other anions having less positive oxidative potential such as iodide, the carrier concentration and the conductivity of the polymer may be effectively increased. A similar effect may also be achieved by using appropriate n- dopants.

EXAMPLE 7: Use of Polymer 2 in a quantum dot LED

Polymer 2 (pNDIBPy.I.) has been used as the electron transport layer (ETL) in a quantum dot light-emitting diode (LED) in an inverted structure. The current density and luminance against voltage is shown in Fig. 9A (control) and 9B (pNDIBPy.I.). ZnO was used as a control, and it can be seen that pNDIBPy.I. out-performs ZnO.

COMPARATIVE EXAMPLE 1: Comparison with pre-existing polymers

Table 1. The inventive polymer in comparison with pre-existing polymers

Table 1 shows a comparison of Polymer 1 with pre-existing polymers such as PNDI2T, BBL and CN- PPV which were obtained from Sigma- Aldrich. It can be seen that the pre-existing polymers which do not fall under the scope of the present application have poorer characteristics compared to that of the inventive polymer, having lower conductivity and in some cases not being stable in air when n-doped. Industrial Applicability

The polymer as disclosed herein is may be useful as an n-type conductive polymer, and may have use in almost all p-n junctions, polymer/hybrid thermoelectrics, as a polymer cathode for batteries and supercapacitors and in quantum dot LEDs.

It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.

Claims

1. A polymer having repeating units of the following Formula (I);

wherein Q is a bond, an optionally substituted aryl or an optionally substituted heteroaryl,

A¹ and A² are independently hydrogen, halogen or an optionally substituted alkyl, or any two A¹ may optionally be taken together to form an optionally substituted aryl;

Ar is an optionally substituted electron deficient aryl that is N-conjugated directly to the pyridyl group,

Y is a counterion, and n is an integer ranging from 5 to 100.

2. The polymer according to claim 1, having repeating units of the following Formula (la);

The polymer according to claim 1 or 2, wherein Ar is N-conjugated directly to the pyridyl group without any linkers.

The polymer according any one of the preceding claims, wherein the structure of Ar comprises a group selected from the group consisting of aryl imide, aryl diimide, aryl diketone and aryl tetraketone.

5. The polymer according to any one of the preceding claims, wherein the structure of Ar comprises a group selected from the group consisting of Formula (Ha), (lib), (lie) and (lid):

wherein R¹ is optionally substituted alkyl,

Z is O or S, and— is a single bond or where the compound of Formulae (Ila), (lib), (lie) or (lid) is fused to the rest of Ar.

The polymer according to claim 5, wherein the group of Formula (Ila), (lib), (lie) or (lid) is independently optionally fused to an optionally substituted aryl.

The polymer according to any one of the preceding claims, wherein Ar is selected from the group consisting of:

wherein R¹ and R² are independently optionally substituted alkyl, and the bond broken is where the Ar is N-conjugated directly to the 4,4'-bipyridyl group.

8. The polymer according to any one of claims 5 to 7, wherein R¹ and R² are independently linear or branched Ci to C₂o alkyl.

9. The polymer according to any one of the preceding claims, wherein Y is selected from the group consisting of CI, Br, I, F, hydroxide, tosylate, gluconate, lactate, acetate, formate, pyruvate, galacturonate, nitrile, trifluoroacetate, nitrate, glutarate, succinate, carbonate, tartrate, benzoate, maleate, sulfate, fumarate, sulfonate, p-toluenesulfonate, methanesulfonate, benzensulfonate, phosphate, citrate, tetrafluoroborate, hexafluorophosphate, bis(trifluoromethane)sulfonimide, hexafluoroantimonate and any mixtures thereof.

10. The polymer according to any one of the preceding claims, wherein n is an integer ranging from 10 to 50.

11. The polymer according to any one of the preceding claims, wherein the polymer has the following structure:

12. A method for synthesizing a polymer having repeating units of the following formula (V),

wherein Q is a bond, an optionally substituted aryl or an optionally substited heteroaryl,

Ar is an optionally substituted electron deficient aryl that is N-conjugated directly to the pyridyl group and n is an integer ranging from 5 to 100; the method comprising the step of contacting a compound having the following Formula (Ilia):

with a compound having the following Formula (Illb): X-Ar-X (Illb), wherein X is a leaving group; under reaction conditions.

13. The method according to claim 12, wherein the compound of Formula (Illb) is 4,4'- bipyridine, and the polymer is selected to have repeating units of the following formula (Va):

14. The method according to claim 12 or 13, comprising the step of N-conjugating the Ar directly to the pyridyl group without any linkers.

15. The method according to any one of claims 12 to 14, wherein the structure of Ar is selected to comprise a group selected from the group consisting of aryl imide, aryl diimide, aryl diketone and aryl tetraketone.

16. The method according to any one of claims 12 to 15, wherein the structure of Ar is selected to comprise a group selected from the group consisting of Formula (Ila), (lib), (lie) and (lid):

wherein R¹ is optionally substituted alkyl, Z is O or S, and— is a single bond or where the compound of Formulae (Ila), (lib), (lie) or (lid) is fused to the rest of Ar.

17. The method according to claim 16, wherein the group of Formula (Ila), (lib), (lie) or (lid) is selected to be independently optionally fused to an optionally substituted aryl.

18. The method according to any one of claims 12 to 17, wherein Ar is selected from the group consisting of:

19. The method according to any one of claims 16 to 18, wherein R¹ and R² are independently selected to be linear or branched Ci to C₂o alkyl.

20. The method according to any one of claims 12 to 19, wherein X is selected to be a weak base.

21. The method according to any one of claims 12 to 20, wherein X is selected from the group consisting of CI, Br, I, tosylate, sulfonate, p-toluenesulfonate, and methane sulfonate .

22. The method according to any one of claims 12 to 21, wherein the polymer

following structure:

23. The method according to any one of claims 12 to 22, wherein the step of contacting the compound of Formula (Ilia) and (Illb) is performed at a temperature in the range of about 100 °C to about 170 °C and for a duration of about 48 hours to about 96 hours.

24. The method according to any one of claims 12 to 23, further comprising a purification step to remove solids having a molecular weight of less than about 3000.

25. The method according to any one of claims 12 to 24, further comprising the step of performing anion exchange to obtain a polymer having repeating units of the following Formula (I):

wherein Y is selected from the group consisting of CI, Br, I, F, hydroxide, tosylate, gluconate, lactate, acetate, formate, pyruvate, galacturonate, nitrile, trifluoroacetate, nitrate, glutarate, succinate, carbonate, tartrate, benzoate, maleate, sulfate, fumarate, sulfonate, p-toluenesulfonate, methane sulfonate, benzensulfonate, phosphate, citrate, tetrafluoroborate , hexafluorophosphate , bis(trifluoromethane) sulfonimide , hexafluoroantimonate and any mixtures thereof.

The use of a polymer according to any one of claims 1 to 1 1 as a conducting polymer.