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WO2018021970A1 - Dérivés conjugués de polyviologène - Google Patents

Dérivés conjugués de polyviologène Download PDF

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Publication number
WO2018021970A1
WO2018021970A1 PCT/SG2017/050378 SG2017050378W WO2018021970A1 WO 2018021970 A1 WO2018021970 A1 WO 2018021970A1 SG 2017050378 W SG2017050378 W SG 2017050378W WO 2018021970 A1 WO2018021970 A1 WO 2018021970A1
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Prior art keywords
group
optionally substituted
polymer
aryl
alkyl
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Inventor
Teck Lip Dexter Tam
Aung Ko Ko Kyaw
Jishan WU
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Agency for Science Technology and Research Singapore
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Agency for Science Technology and Research Singapore
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines

Definitions

  • 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.
  • 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.
  • HTL hole-transporting layer
  • ETL electron-transporting layer
  • 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.
  • a 1 and A 2 are independently hydrogen or an optionally substituted alkyl, or any two A 1 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.
  • 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.
  • 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.
  • a 1 and A 2 are independently hydrogen or an optionally substituted alkyl, or any two A 1 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 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):
  • 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.
  • 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.
  • the polymer may be useful in any p-n junction, hybrid thermoelectrics and polymer cathode for batteries or supercapacitors.
  • 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.
  • alkyl alkyl
  • alkylene alkylene
  • 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 C 1 -C25 alkyl, more preferably a C 1 -C 10 alkyl, most preferably Ci-C 6 unless otherwise noted.
  • suitable straight and branched Ci-C 6 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) 2 N- 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-C 6 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.
  • the alkyloxy is a Ci-C 6 alkyloxy. 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 a R 3 ⁇ 4 wherein R a and R 3 ⁇ 4 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.
  • aryl groups include phenyl, naphthyl, and the like; (ii) an optionally substituted partially saturated bicyclic aromatic carbocyclic moiety in which a phenyl and a C 5 _ 7 cycloalkyl or C 5 _ 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.
  • an aryl group is a C 3 -Ci 8 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 C 3 -Ci 2 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 C 3 -Ci 2 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 n H (2 n + i-m)Xm wherein each X is independently selected from the group consisting of F, CI, Br and I .
  • 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.
  • heteroalkyl also include hydroxyCi-C 6 alkyl, Ci-C 6 alkyloxyCi-C 6 alkyl, aminoCi-C 6 alkyl, Ci-C 6 alkylaminoCi-C 6 alkyl, and di(Ci-C 6 alkyl)aminoCi-C 6 alkyl.
  • 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.
  • heteroaryl examples 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, phen
  • 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.
  • 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.
  • optionally substituted 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, cycloal
  • Viologen 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 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.
  • 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.
  • FIG. 1 is a schematic diagram showing how the inventive polymer is prepared.
  • Fig. 2 is a schematic diagram showing how the inventive polymer is prepared.
  • FIG. 2 is the 3 ⁇ 4 NMR spectrum of Polymer 1 (pNDIBPy.Br).
  • Fig. 3 is the 3 ⁇ 4 NMR spectrum of Polymer 1 (pNDIBPy.Br).
  • FIG. 3 is the 3 ⁇ 4 NMR spectrum of Polymer 2 (pNDIBPy.I).
  • Fig. 4 is the 3 ⁇ 4 NMR spectrum of Polymer 2 (pNDIBPy.I).
  • FIG. 4 is the UV-Vis-NIR spectrum of Polymers 1 and 2.
  • Fig. 5 is the UV-Vis-NIR spectrum of Polymers 1 and 2.
  • FIG. 5 is a graph showing the sheet resistance of Polymer 1 over 14 days.
  • Fig. 6 is a graph showing the sheet resistance of Polymer 1 over 14 days.
  • FIG. 6 is a diagram showing the electron conductivity of the inventive polymers compared to pre-existing compounds
  • FIG. 7 is a graph showing the cyclic voltammetry of Polymer 1.
  • Fig. 8 is a graph showing the cyclic voltammetry of Polymer 1.
  • FIG. 8 is a schematic representation showing the LUMO of Polymer 1.
  • 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).
  • LED quantum dot light- emitting diode
  • ETL electron transport layer
  • 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:
  • a 1 and A 2 may independently be hydrogen, halogen or an optionally substituted alkyl, or any two A 1 may optionally be taken together to form an optionally substituted aryl.
  • a 1 and A 2 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.
  • R 1 may be optionally substituted alkyl.
  • R 1 may be a Ci to C 20 alkyl.
  • R 1 may be Ci to C 5 alkyl, Ci to Cio alkyl, Ci to Ci 5 alkyl, C 5 to Cio alkyl, C 5 to Ci 5 alkyl, C 5 to C 20 alkyl, Cio to Ci 5 alkyl, Cio to C 20 alkyl or Ci 5 to C 2 o alkyl.
  • R 1 may be linear or branched.
  • R 1 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 R 1 is attached to Formula (Ila) or (lib), h may be 1, i may be 2 and j may be 4.
  • R 1 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
  • 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.
  • Formulae (Ila), (lib), (lie) and (lid) may have the following Formula (Ila'), (lib'), (lie') or (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:
  • R 1 is attached to Formula (Ila) or (lib).
  • Ar or the electron deficient aryl may be optionally substituted.
  • R 1 and R 2 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.
  • R 1 and R 2 may both be an optionally substituted alkyl.
  • R 1 and R 2 may independently be Ci to C 20 alkyl, Ci to C 5 alkyl, Ci to Cio alkyl, Ci to Ci 5 alkyl, C 5 to Cio alkyl, C 5 to Ci 5 alkyl, C 5 to C 20 alkyl, Cio to Ci 5 alkyl, Cio to C 20 alkyl or Ci 5 to C 2 o alkyl.
  • R 1 and R 2 may independently be linear or branched.
  • R 1 and R 2 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.
  • R 1 and R 2 may be independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
  • R 1 and R 2 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,
  • 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
  • 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.
  • 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:
  • a 1 and A 2 may independently be hydrogen, halogen or an optionally substituted alkyl, or any two A 1 may optionally be taken together to form an optionally substituted aryl.
  • a 1 and A 2 may independently be hydrogen or fluorine.
  • 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):
  • 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):
  • 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.
  • R 1 may be optionally substituted alkyl.
  • R 1 may be a Ci to C 20 alkyl.
  • R 1 may be Ci to C 5 alkyl, Ci to Cio alkyl, Ci to Ci 5 alkyl, C 5 to Ci 0 alkyl, C 5 to Ci 5 alkyl, C 5 to C 20 alkyl, Ci 0 to Ci 5 alkyl, Ci 0 to C 20 alkyl or Ci 5 to C 2 o alkyl.
  • R 1 may be linear or branched.
  • R 1 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 R 1 is attached to Formula (Ila) or (lib). h may be 1, i may be 2 and j may be 4.
  • R 1 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-methylhepty
  • 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.
  • Formulae (Ila), (lib), (lie) and (lid) may have the following Formula (Ila'), (lib'), (lie') or (lid'):
  • 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:
  • R 1 is attached to Formula (Ila) or (lib).
  • Ar or the electron deficient aryl may be optionally substituted.
  • R 1 and R 2 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.
  • R 1 and R 2 may both be an optionally substituted alkyl.
  • R 1 and R 2 may independently be Ci to C 20 alkyl, Ci to C 5 alkyl, Ci to Cio alkyl, Ci to Ci 5 alkyl, C 5 to Cio alkyl, C 5 to Ci 5 alkyl, C 5 to C 20 alkyl, Cio to Ci 5 alkyl, Cio to C 20 alkyl or Ci 5 to C 2 o alkyl.
  • R 1 and R 2 may independently be linear or branched.
  • R 1 and R 2 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.
  • R 1 and R 2 may be independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.
  • R 1 and R 2 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- dimethylpenty
  • 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):
  • 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.
  • 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:
  • 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.
  • Br 2 -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.
  • 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 (Br 2 -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.
  • Polymer 2 was prepared by as shown in Fig. 1. I 2 -NDI. 500 mg of 2,6-dibromo-N,N-bis(2-ethylhexyl)-l,8:4,5-naphthalene tetracarboxdiimide (Br 2 - 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 conjugated polyviologen thin film of polymer 1 having a thickness of approximately 70 nm gave sheet resistance of approximately 6 x 10 6 ⁇ /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.
  • the measured electron conductivity of the polymer was found to be higher than some of the commercial grade p-type conducting PEDOT:PSS.
  • charge transport interlayer material normally has a conductivity in the range of 10 "6 to 1 Scm “1 (CleviosTM 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.
  • 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).
  • LUMO lowest unoccupied molecular orbital
  • 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.
  • DFT Density Functional Theory
  • the HOMO localized on the atomic orbitals of bromine while the LUMO is located on the polymer backbone.
  • 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.
  • PCBM phenyl-C61 -butyric acid methyl ester
  • 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.
  • 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.
  • 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.
  • ETL electron transport layer
  • LED quantum dot light-emitting diode
  • Fig. 9A control
  • 9B pNDIBPy.I.
  • ZnO was used as a control, and it can be seen that pNDIBPy.I. out-performs ZnO.
  • 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.
  • 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.

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Abstract

La présente invention concerne un polymère conjugué de type accepteur-accepteur qui est un polymère conducteur de type n ayant la formule (I) suivante : dans laquelle Q est une liaison, un aryle éventuellement substitué ou un hétéroaryle éventuellement substitué ; A1 et A2 sont indépendamment l'hydrogène, un halogène ou un alkyle éventuellement substitué, ou deux A1 quelconques peuvent facultativement être pris ensemble pour former un aryle éventuellement substitué ; Ar est un aryle déficient en électrons éventuellement substitué qui est N-conjugué directement au groupe pyridyle ; Y est un contre-ion ; et n est un nombre entier allant de 5 à 100. Le polymère de formule (I) présente une faible valeur LUMO, ainsi qu'une conductivité électronique et une stabilité à l'air ou à l'oxygène élevées. La présente invention concerne également un procédé de synthèse dudit polymère, et l'utilisation dudit polymère. Dans un mode de réalisation préféré, du 2,6-dibromo-N,N'-bis(2-éthylhexyl)-1,8:4,5-naphtalène tétracarboxdiimide a été mis en réaction avec de la 4,4'-bipyridine pour former un dérivé conjugué de polyviologène dans lequel le motif viologène est lié directement par covalence à un accepteur d'électron aromatique par l'intermédiaire des atomes d'azote.
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US11271238B2 (en) * 2018-11-27 2022-03-08 Utah State University Applications of low-cost, thermal and electrochemically stable organic compounds as high performance redox active materials in redox flow batteries
US12527733B2 (en) 2021-08-08 2026-01-20 Elc Management Llc Fragrance compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11271238B2 (en) * 2018-11-27 2022-03-08 Utah State University Applications of low-cost, thermal and electrochemically stable organic compounds as high performance redox active materials in redox flow batteries
US12527733B2 (en) 2021-08-08 2026-01-20 Elc Management Llc Fragrance compositions

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