Polymer hole transport material and application thereof

Abstract

The invention discloses a plurality of polymer hole transport materials which are applied to an inverted perovskite solar cell, have high affinity to perovskite ink, are simple and convenient to process, and endow the perovskite solar cell with excellent photoelectric properties.

Description

[0001] Cross-reference to related applications

[0002] This invention claims priority and benefit to U.S. Provisional Patent Application No. 63 / 659,155, filed June 12, 2024, the disclosure of which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention relates to polymer hole transport materials and their application in perovskite solar cell devices. Background Technology

[0004] Perovskite solar cells (PSCs) are a type of solar cell that comprises perovskite-structured compounds, most commonly a mixture of organic-inorganic lead or tin halide-based materials as the light-collecting active layer. PSCs are highly promising due to their high efficiency, ease of integration into cascaded devices, and the potential for low-cost manufacturing through relatively simple processes (such as roll-to-roll printing).

[0005] Generally, PSCs can be divided into two architecture types: NIP and PIN, with the difference determined by the deposition sequence of electron- and hole-selective contacts relative to the transparent conductive oxide (TCO) substrate. PSCs include hole-transport materials (HTMs), which play a crucial role in device stability and efficiency by promoting hole extraction and suppressing charge recombination between the anode and perovskite layers, while also aiding in charge separation and hole conduction to the PSC's cathode. For example, the fabrication of PIN devices allows light to pass through a multi-layered structure, including a glass protective layer, anode, and HTM, before being absorbed by the active perovskite layer.

[0006] The material of HTM is often chosen from organic materials due to their tunable thermal and optoelectronic properties, and suitability for vacuum and / or solution processing. Small molecules and polymers containing triarylamine moieties are common choices, which can be modified to meet device requirements. In particular, (poly)arylamines are common choices for HTM in PSCs due to their electron-rich nature and high excited state stability, which arise from the resonance of the adjacent conjugated groups of (poly)arylamines. Currently, potential materials for NIP and PIN devices are poly[bis(4-phenyl)-(2,4,6-trimethylphenyl)amine] (PTAA), 2,2',7,7'-tetra[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz), and poly(3-hexylthiophene-2,5-diyl) (P3HT).

[0007] HTM is a component of many diode devices, such as solar (e.g., PSC), OLED, photodetector, and laser, etc. Current HTMs lack the ability to meet the required properties for these applications, such as high glass transition temperature (higher than 150 °C), tunable energy levels (i.e., HOMO, LUMO) to match adjacent layers in the device, high passivation ability to address defects at the HTM perovskite interface, and sufficient wetting to allow ohmic contact of adjacent layers in the device.

[0008] Therefore, there is a need in the art for a new hole-transport material (HTM) that can be easily tuned for different perovskites, has high affinity for perovskite inks, is simple to process (e.g., solution-processed), and imparts superior optoelectronic properties to perovskite solar cells. SUMMARY

[0009] In a first embodiment, the present disclosure discloses a first polymeric hole-transport material comprising a copolymer based on triarylamine monomers and carbazole monomers, the triarylamine monomers having the following general structure:

[0010]

[0011] wherein R1is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (CI), bromine (Br), iodine (I), cyano (CN), vinyl, acid, or a combination thereof;

[0012] R2is independently a linear or branched alkyl chain, wherein one or more hydrogen (H) atoms are optionally substituted with fluorine (F), chlorine (CI), bromine (Br), iodine (I), or cyano (CN).

[0013] The carbazole monomer comprises an alkyl chain directly bonded to the nitrogen atom of the carbazole structure, the alkyl chain having 1 to 11 carbon atoms, and further having an X terminal and a Y terminal, wherein X is hydrogen (H) or cyano (CN), and Y is selected from the following group:

[0014]

[0015] In a second embodiment, the present disclosure discloses a second polymeric hole transport material, the second polymeric hole transport material comprising a polymer based on a benzene monomer or a fluorene monomer or a combination thereof, the benzene monomer or the fluorene monomer selected from the following group:

[0016]

[0017] wherein R is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (CI), bromine (Br), iodine (I), cyano (CN), vinyl, acid, or a combination thereof.

[0018] In a third embodiment, the present disclosure discloses a third polymeric hole transport material, the third polymeric hole transport material comprising a polymer based on a fused carbazole monomer, the fused carbazole monomer selected from the following group:

[0019]

[0020] wherein X is independently selected from hydrogen (H) or cyano (CN);

[0021] n is independently selected from an integer from 0 to 10; and

[0022] Y is independently selected from the following group:

[0023]

[0024] In a fourth embodiment, the present disclosure discloses a fourth polymeric hole transport material, the fourth polymeric hole transport material comprising a conjugated polymer having one or more repeating units, the repeating unit having at least one phosphoric acid group [P(0)(OH)2] and at least one cyano group (C≡N) on the same side chain.

[0025] In a fifth embodiment, the present disclosure discloses an inverted perovskite solar cell having a p-i-n structure, the inverted perovskite solar cell comprising a hole transport layer comprising the first or the second or the third or the fourth polymeric hole transport material.

[0026] Preferably, the inverted perovskite solar cell can be a single-junction solar cell, or at least one sub cell included in a multi-junction solar cell.

[0027] Preferably, the inverted perovskite solar cell can be arranged as an inverted perovskite sub cell on a silicon heterojunction sub cell in a tandem solar cell.

[0028] The above description is only a summary of the technical solutions of the present application. The complete embodiments of the present application are provided below to make those of ordinary skill in the art more easily understand the operation process of the present application and its purposes, characteristics and advantages. DETAILED DESCRIPTION

[0029] Definitions

[0030] The use of the terms "including", "comprising", "having" or "with" should be generally accepted as open-ended and non-limiting, unless otherwise explicitly noted.

[0031] The use of the singular herein will be understood to encompass the plural, and vice versa, unless explicitly stated otherwise. Further, the description herein including the use of the term "about" before quantitative values is intended to encompass the specific quantitative value itself, unless explicitly stated otherwise. The term "about" as used herein means within ±10% of the stated value, unless otherwise stated or inferred.

[0032] The order of description of the steps of any method is not intended to be construed as a limitation, unless explicitly stated otherwise. Furthermore, two or more steps can be conducted simultaneously.

[0033] As used herein, "environmentally stable" or "stable under ambient conditions" means that a compound can be considered "environmentally stable" or "stable under ambient conditions" when the carrier mobility of a transistor having the compound as its semiconductor material remains within about 20% or 10% of the initial measured value when the transistor is exposed to ambient conditions (e.g., air, ambient temperature, and humidity) for a period of time. For example, a compound can be described as environmentally stable if the carrier mobility of a transistor containing the compound does not change by more than 20% or 10% from its initial value after exposure to ambient conditions (including air, humidity, and temperature) for 3 days, 5 days, or 10 days.

[0034] As used herein, "fill factor (FF)" is the ratio (expressed in percentage) of the actual maximum obtainable power (Pm or Vmp*Jmp) to the theoretical (practically unobtainable) power (Jsc*Voc). Thus, FF can be determined using the following equation:

[0035] FF = (Vmp*Jmp) / (Jsc*Voc)

[0036] where Jmp and Vmp represent the current density and voltage at the maximum power point (Pm), respectively, which is obtained by varying the resistance in the circuit until J*V reaches its maximum value; Jsc and Voc represent the short-circuit current and open-circuit voltage, respectively. Fill factor is a key parameter for evaluating the performance of a solar cell. Commercial solar cells typically have a fill factor of about 0.60% or greater.

[0037] As used herein, "open-circuit voltage (Voc)" is the potential difference between the anode and cathode of a device when no external load is connected.

[0038] As used herein, "power conversion efficiency (PCE) of a solar cell" is the percentage of power converted from absorbed light to electrical energy. The PCE of a solar cell can be calculated by dividing the maximum power point (Pm) by the input light irradiance (E, in W / m 2 ) under standard test conditions (STC) and the surface area of the solar cell (Ac, in m 2 ). STC typically refers to a temperature of 25 °C, an irradiance of 1000 W / m 2 , and an air mass spectrum of 1.5 (AM 1.5).

[0039] As used herein, "solution processable" refers to a compound (such as a polymer), material, or composition that can be used in various solution-phase processes, including spin coating, printing (such as inkjet printing, gravure printing, offset printing, etc.), spray coating, electrospray coating, drop casting, dip coating, blade coating, etc.

[0040] As used herein, "polymeric compound" or "polymer" refers to a molecule comprising a plurality of one or more repeating units connected by covalent chemical bonds. A polymer can be represented by general formula I:

[0041] *-(-(Ma)x-(Mb)y-)z*

[0042] General Formula I

[0043] where each Maand Mbis a repeat unit or monomer. The polymeric compound can have only one type of repeat unit and two or more types of different repeat units. When the polymer has only one type of repeat unit, it can be referred to as a homopolymer. When the polymeric compound has two or more different repeat units, the term “copolymer” or “co-polymeric compound” can be used in its place. For example, a co-polymeric compound can include repeat units where Maand Mbdenote two different repeat units. Unless otherwise specified, the assembly of repeat units in a copolymer can be head-to-head, head-to-tail, or tail-to-tail. Further, unless otherwise specified, a copolymer can be a random copolymer, an alternating copolymer, or a block copolymer.

[0044] For example, general formula I can be used to represent a copolymer of Maand Mbwith x mole fraction of Maand y mole fraction of Mb, where the repeat of the comonomers Maand Mbmay be alternating, random, region-random, or region-regular, or blocky, with up to z comonomers. In addition to its composition, a polymer can be further characterized by its degree of polymerization (n) and molar mass [e.g., number average molecular weight (Mn) and / or weight average molecular weight (Mw), depending on the measurement technique].

[0045] As used herein, “alkyl” refers to a straight-chain or branched-chain saturated hydrocarbon group. Examples of alkyl groups include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and i-propyl), butyl (e.g., n-butyl, i-butyl, sec-butyl, t-butyl), pentyl (e.g., n-pentyl, i-pentyl, neopentyl, t-pentyl), hexyl, and the like. In various embodiments, an alkyl group can have 1 to 40 carbon atoms (i.e., C1-C40 alkyl), for example, 1-30 carbon atoms, i.e., C1-C30 alkyl. In some embodiments, an alkyl group can have 1 to 6 carbon atoms, and can be referred to as a “lower alkyl.” Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and i-propyl), and butyl (e.g., n-butyl, i-butyl, sec-butyl, t-butyl). In some embodiments, an alkyl group can be substituted as described herein. An alkyl group is typically not substituted with another alkyl, alkenyl, or alkynyl group.

[0046] As used herein, “fused ring” or “fused ring moiety” refers to a polycyclic ring system having at least two rings, at least one of which is an aromatic ring, and where such aromatic ring (carbocyclic or heterocyclic) has a common bond to at least one other ring (which can be aromatic or non-aromatic, and carbocyclic or heterocyclic). These polycyclic ring systems can be highly p conjugated, and can be substituted as described herein.

[0047] In a first embodiment, the present application provides a first polymeric hole transport material comprising a copolymer based on a triarylamine monomer and a carbazole monomer, the triarylamine monomer having the following general formula:

[0048]

[0049] wherein R1 is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), cyano (CN), vinyl, acid, or a combination thereof;

[0050] R2 is independently a straight or branched alkyl chain, wherein one or more hydrogen (H) atoms are optionally substituted with fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or cyano (CN).

[0051] The carbazole monomer comprises an alkyl chain directly bonded to the nitrogen atom of the carbazole structure, the alkyl chain having 1 to 11 carbon atoms, and further having an X terminal end and a Y terminal end, wherein X is hydrogen (H) or cyano (CN), and Y is selected from the following groups:

[0052]

[0053] Further, the carbazole monomer can be selected from the following groups:

[0054]

[0055] wherein X is independently selected from hydrogen (H) or cyano (CN);

[0056] n is independently selected from an integer from 0 to 10; and

[0057] Y is independently selected from the following groups:

[0058]

[0059] Preferably, X is hydrogen (H), and Y is

[0060] The triarylamine monomer is selected from the following groups:

[0061]

[0062] wherein X is independently selected from hydrogen (H) or cyano (CN);

[0063] n is independently selected from an integer from 0 to 10; and

[0064] Y is independently selected from the following groups:

[0065]

[0066] In this embodiment, the ratio of the triarylamine monomer to the carbazole monomer is from 0.2 to 5.

[0067] In this embodiment, the average molecular weight of the copolymer is in the range of about 1,000 to about 1,000,000 Da.

[0068] In a second embodiment, the present application provides a second polymeric hole transport material comprising a polymer based on benzene monomers or fluorene monomers or a combination thereof (hereinafter referred to as Polymer A), the benzene monomers or fluorene monomers are selected from the following groups:

[0069]

[0070] wherein R is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (CI), bromine (Br), iodine (I), cyano (CN), vinyl, acid, or a combination thereof.

[0071] Further, the benzene monomers can be selected from the following groups:

[0072]

[0073] wherein X is independently selected from hydrogen (H) or cyano (CN);

[0074] n is independently selected from an integer from 0 to 10; and

[0075] Y is independently selected from the following groups:

[0076]

[0077] Preferably, X is hydrogen (H) and Y is

[0078] In a preferred example, the benzene monomers have the following general structure:

[0079]

[0080] In this embodiment, Polymer A can be a homopolymer or a copolymer. The average molecular weight of Polymer A is in the range of about 1,000 to about 1,000,000 Da.

[0081] Further, the second polymeric hole transport material can employ other monomers to prepare a polymer (hereinafter referred to as Polymer B) to meet the required performance of perovskite solar cells. Polymer B comprises a copolymer based on monomer I and monomer II, monomer I is benzene monomers or fluorene monomers or a combination thereof, the benzene monomers or fluorene monomers are selected from the following groups:

[0082]

[0083] wherein R is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (CI), bromine (Br), iodine (I), cyano (CN), vinyl, acid, or a combination thereof.

[0084] Monomer II is a triarylamine monomer or a carbazole monomer or a combination thereof, the triarylamine monomer having the following general structural formula:

[0085]

[0086] wherein R1is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (CI), bromine (Br), iodine (I), cyano (CN), vinyl, an acid, or a combination thereof;

[0087] R2is independently a linear or branched alkyl chain, wherein one or more hydrogen (H) atoms are optionally substituted with fluorine (F), chlorine (CI), bromine (Br), iodine (I), or cyano (CN); and

[0088] The carbazole monomer comprises an alkyl chain directly bonded to a nitrogen atom of a carbazole structure, the alkyl chain having 1 to 11 carbon atoms, and further having an X terminal end and a Y terminal end, wherein X is hydrogen (H) or cyano (CN), and Y is selected from the following groups:

[0089]

[0090] Further, the carbazole monomer can be selected from the following groups:

[0091]

[0092] wherein X is independently selected from hydrogen (H) or cyano (CN);

[0093] n is independently selected from an integer from 0 to 10; and

[0094] Y is independently selected from the following groups:

[0095]

[0096] Preferably, X is hydrogen (H), and Y is

[0097] In a third embodiment, the present application provides a third polymeric hole transport material comprising a polymer based on a fused carbazole monomer selected from the following groups:

[0098]

[0099] wherein X is independently selected from hydrogen (H) or cyano (CN);

[0100] n is independently selected from an integer from 0 to 10; and

[0101] Y is independently selected from the following groups:

[0102]

[0103] Preferably, X is hydrogen (H) and Y is

[0104] In this embodiment, the polymer can be a homopolymer or a copolymer. The average molecular weight of the polymer is in the range of about 1,000 to about 1,000,000 Da.

[0105] In a fourth embodiment, the present application provides a fourth polymer hole transport material comprising a conjugated polymer having one or more repeating units, the repeating unit having at least one phosphonic acid group [P(O)(OH)2] and at least one cyano group (C≡N) on the same side chain.

[0106] Preferably, the repeating unit is selected from the following group:

[0107]

[0108] Preferably, the conjugated polymer is substantially free of triarylamine structure and carbazole structure.

[0109] Use in inverted perovskite solar cells (PSCs)

[0110] Inverted perovskite solar cells (PSCs) with p-i-n architecture have attracted extensive attention in both academia and industry due to their compatibility with large-scale production and the potential for enhanced device stability. However, most reports on high-efficiency p-i-n PSCs are usually small-size spin-coated devices fabricated in an inert atmosphere, and further improvement in stability is needed to meet industry standards. Therefore, it is crucial to develop high-efficiency and stable PSCs processed under ambient conditions using coating methods compatible with large-area production.

[0111] To achieve uniform large-area production of p-i-n perovskite solar devices, a key step is to coat perovskite ink on the surface of hole transport material (HTM) by blade or slot-die coating. During the coating process, the wettability, uniformity, and stability of HTM on the transparent conductive oxide (TCO) substrate have a critical impact on the quality of perovskite thin film and the performance of the device. An ideal HTM should not only transport holes with good uniformity, but also promote the coverage and crystallization of perovskite thin film to achieve scalable production, especially under ambient conditions where environmental factors such as moisture and oxygen can have a significant impact on the perovskite crystallization process.

[0112] The most common p-i-n PSCs today use two types of organic HTMs, one is small molecule self-assembled monomer (SAM) such as carbazole phosphonic acid (PACz), and the other is polymeric material such as PTAA. Each of these two types of HTMs has its own advantages and serious drawbacks. First, the process window for the optimal thickness of small molecule PACz SAM is very small, the condition is very stringent, and it has poor uniformity in large area coating. Therefore, engineers in the PSC industry often encounter SAMs that are too thick, resulting in poor hole transport, or partial coverage of the SAM on the bottom electrode, leading to charge recombination at the interface. For the foregoing reasons, SAM-based HTMs are currently not considered a suitable choice by the PSC industry.

[0113] On the other hand, polymeric HTMs such as PTAA can have better coating uniformity and charge transport capability, which can overcome the weaknesses of SAMs. However, the surface of PTAA is too hydrophobic to be suitable for uniform large-area coating of perovskite ink. In addition, PTAA-based PSCs appear to be less efficient than SAM-based devices, which can be due to the lack of phosphonic groups that not only bind to the electrode surface but also provide a passivation effect for the perovskite layer.

[0114] Furthermore, PTAA has a high degree of hydrophobicity to perovskite ink precursors, which often means that an interface layer or post-deposition modification with UV and ozone is required to obtain a satisfactory absorption layer. Therefore, PTAA-based HTMs usually require additional post-deposition processes to improve the wettability of the HTM to the perovskite ink.

[0115] In a fifth embodiment, the present application provides a perovskite solar cell. The perovskite solar cell includes a hole transport layer including the first or second or third or fourth polymeric hole transport material of the above-mentioned embodiments.

[0116] In addition, the perovskite solar cell can be a perovskite solar cell of an inverted structure. The perovskite solar cell can further include a substrate, a perovskite active layer, an electron transport layer, a blocking layer, and a metal electrode. The substrate can be selected from a glass / ITO substrate, a glass / FTO substrate, a PET / ITO substrate, and any combination thereof.

[0117] Single-junction vs. multi-junction solar cells

[0118] A single-junction solar cell uses a single semiconductor material for the p-n junction, while a multi-junction [or tandem] solar cell employs multiple p-n junctions of different materials to absorb different wavelengths of light, thereby improving efficiency.

[0119] Single-junction solar cells are limited in their ability to absorb the full spectrum of sunlight by the single p-n junction formed by doping two semiconductor materials, typically n-type and p-type, which limits their ability to absorb the full spectrum of sunlight, resulting in lower efficiency compared to multi-junction cells.

[0120] Multi-junction (tandem) solar cells employ multiple p-n junctions, each made of a different semiconductor material with a specific bandgap. Each junction absorbs a different range of wavelengths of the solar spectrum, allowing for a wider absorption of sunlight and higher efficiency. Multi-junction solar cells can be designed as tandems (two junctions), triple junctions, quadruple junctions, etc.

[0121] Traditional single-junction solar cells are typically composed of a single semiconductor material, such as single-crystalline or polycrystalline silicon. These materials absorb solar radiation within a specific range and convert it into electrical energy. On the other hand, perovskite tandem solar cells combine perovskite materials with other semiconductor materials, such as silicon, in a layered structure that takes advantage of the light absorption properties of different materials to expand the range of absorption across the entire solar spectrum. This stacked structure allows each material layer to focus on its optimal absorption spectral range, resulting in improved overall light conversion efficiency.

[0122] In a sixth embodiment, the present invention provides an inverted perovskite solar cell having a p-i-n structure, the inverted perovskite solar cell comprising a hole transport layer comprising a first or second or third or fourth polymeric hole transport material.

[0123] Preferably, the inverted perovskite solar cell can be a single-junction solar cell, or at least one sub cell included in a multi-junction solar cell.

[0124] Preferably, the inverted perovskite solar cell can be arranged as an inverted perovskite sub cell on a silicon heterojunction sub cell in a tandem solar cell.

[0125] Example 1 - Synthesis of CT-1, CT-2, and CT-3 copolymers

[0126]

[0127] preCT-1:

[0128] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 eq), 2,2’-bipyridine (263 mg, 1.70 mmol, 1.0 eq) and cyclooctadiene (184 mg, 1.70 mmol, 1.0 eq) was added 25 mL of anhydrous degassed DMF under nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 min. Subsequently, a solution of (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)diethyl phosphonate (274 mg, 0.53 mmol, 0.3 eq) and N,N-bis(4-bromophenyl)-2,4,6-trimethylbenzenamine (236 mg, 0.53 mmol, 0.3 eq) in 6 mL of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature, pH was adjusted to 1-2 by adding 1 M HC1. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2S04and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to obtain 250 mg of preCT-1 as a light grey solid in 76% yield. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.40 (s), 7.90 (s), 7,42 (m), 7.09 (m), 6.77 (s), 4.33 (m), 2.22 (m), 1.40 (m), 1.26 (m).; SEC data: M n = 10.1 x 10 3 g mol –1 ,

[0129] CT-1:

[0130] To a solution of preCT-1 (60 mg) in 11 mL of anhydrous CH2Cl2was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2under nitrogen atmosphere. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH, the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether, a second precipitation and filtration were performed to obtain 50 mg of CT-1 as a white solid in 91% yield. 1H-NMR (CDCl3 and CD3OD, 400MHz) δ (ppm): 8.40 (s), 7.90 (m), 7.09 (m), 6.77 (s), 4.90 (m), 4.01 (m), 2.34 (m), 1.26 (m).

[0131] preCT-2:

[0132] The synthetic route for preCT-2 was similar to that of preCT-1, except that it used a solution of (4-(3,6-dibromo-9H-carbazole-9-yl)butyl)phosphonate (181 mg, 0.35 mmol, 0.21 equivalents) and N,N-bis(4-bromophenyl)-2,4,6-trimethylaniline (312 mg, 0.70 mmol, 0.42 equivalents) in 6 mL of anhydrous DMF. The resulting mixture was stirred at 80 °C for 18 hours. It was then cooled to room temperature, and the pH was adjusted to 1–2 with 1 M HCl. The resulting mixture was extracted with CH₂Cl₂, and the organic layer was washed three times with 1 M HCl. The organic layer was dried over anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was dissolved in a minimal amount of CH₂Cl₂ and added dropwise to a vigorously stirred solution of diethyl ether for 1–2 hours, or until a precipitate formed. The obtained polymer was filtered and washed with diethyl ether to give 234 mg of preCT-2 in the form of a light gray solid, with a yield of 72%. 1 H-NMR (CDCl3, 400MHz) δ (ppm): 8.41 (s), 7.89 (s), 7, 42 (m), 7.09 (m), 6.77 (s), 4.33 (m), 2.22 (m), 1.40 (m), 1.26 (m).; SEC data: M n =12.1×10 3 g mol –1 ,

[0133] CT-2:

[0134] The synthetic route for CT-2 was similar to that for CT-1, except that a solution of preCT-2 (60 mg) in 11 mL of anhydrous CH2Cl2 was used. The reaction mixture was kept at 25 °C for 18 hours. The resulting mixture was quenched with 8 mL of MeOH, and the reaction mixture was stirred at room temperature for 12 hours. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimal amount of CH2Cl2 and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1–2 hours, or until a precipitate formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to give 47 mg of white solid CT-2 in 84% yield. 1H-NMR (CDCl3 and CD3OD, 400MHz) δ (ppm): 8.43 (s), 7.87 (br, m), 7.12 (m), 6.78 (s), 4.97 (m), 4.01 (m), 2.34 (m), 1.26 (m).

[0135] preCT-3:

[0136] The synthetic route for preCT-3 was similar to that for preCT-1, except that it used a solution of (4-(3,6-dibromo-9H-carbazole-9-yl)butyl)phosphonate (140 mg, 0.27 mmol, 0.16 equivalents) and N,N-bis(4-bromophenyl)-2,4,6-trimethylaniline (356 mg, 0.80 mmol, 0.47 equivalents) in 6 mL of anhydrous DMF. The resulting mixture was stirred at 80 °C for 18 hours. It was then cooled to room temperature, and the pH was adjusted to 1–2 with 1 M HCl. The resulting mixture was extracted with CH₂Cl₂, and the organic layer was washed three times with 1 M HCl. The organic layer was dried over anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was dissolved in a minimal amount of CH₂Cl₂ and added dropwise to a vigorously stirred solution of diethyl ether for 1–2 hours, or until a precipitate formed. The obtained polymer was filtered and washed with diethyl ether to give 219 mg of light gray solid preCT-3, with a yield of 67%. 1 H-NMR (CDCl3, 400MHz) δ (ppm): 8.40 (s), 7.91 (s), 7, 42 (m), 7.10 (m), 6.77 (s), 4.35 (m), 2.29 (m), 1.40 (m), 1.28 (m).; SEC data: M n =12.8×10 3 g mol –1 ,

[0137] CT-3:

[0138] The synthetic route for CT-3 was similar to that for CT-1, except that a solution of preCT-3 (60 mg) in 11 mL of anhydrous CH2Cl2 was used. The reaction mixture was kept at 25 °C for 18 hours. The resulting mixture was quenched with 8 mL of MeOH, and the reaction mixture was stirred at room temperature for 12 hours. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimal amount of CH2Cl2 and MeOH, and the resulting solution was added dropwise to a vigorously stirred ether solution for 1–2 hours, or until a precipitate formed. The resulting polymer was filtered and washed with ether, and the precipitation and filtration were repeated twice to give 53 mg of white solid CT-2 in 93% yield. 1H-NMR (CDC13, 400 MHz) δ (ppm): 8.50 (s), 7.67 (m), 7,42 (m), 6.99 (s), 4.30 (m), 2.99 (m), 1.92 (m), 1.28 (m); SEC data: Mw= 7.8 x 105, Mw / Mn= 1.2, Mz / Mw= 1.3.

[0139] Example 2 - Synthesis of CP copolymers

[0140]

[0141] preCP:

[0142] To a mixture of diethyl (2-(3,6-bis(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-9H- carbazol-9-yl)ethyl)phosphonate (292 mg, 0.5 mmol, 1.0 equiv), tetraethyl((2,5-dibromo- 1,4-phenylene)bis(ethane-2, 1 -diyl))bis(phosphonate) (282 mg, 0.5 mol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium(0) (13 mg, 0.014 mmol, 3 mol%), 2- dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) (25 mg, 0.06 mmol, 12 mol%) was added, and 5 mL of dioxane and 2 mL of water was added to potassium phosphate (425 mg, 2.0 mmol, 4 equiv) under N2atmosphere. The resulting mixture was refluxed under the same N2atmosphere for 15 hours. The resulting mixture was extracted with CH2Cl2, the organic layer was dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 hours, or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to obtain 187 mg of preCP as a gray solid with a yield of 51%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.50 (s), 7.67 (m), 7,42 (m), 6.99 (s), 4.30 (m), 2.99 (m), 1.92 (m), 1.28 (m); SEC data: Mw= 7.8 x 105, Mw / Mn= 1.2, Mz / Mw= 1.3. n = 7.8 x 105 3 g mol –1 ,

[0143] CP:

[0144] To a solution of preCP (100 mg) in 20 mL of anhydrous CH2Cl2under a nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to obtain 74 mg of a gray solid CP with a yield of 95%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.38 (s), 8.20 (m), 7.64 (m), 4.28 (m), 2.05 (m), 1.92 (m), 1.32 (m); SEC data: Mn= 9.2 x 10

[0145] Example 3 - Synthesis of CPCN copolymers

[0146]

[0147] preCPCN:

[0148] To a solution of (2-(3,6-bis(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-9H-carbazol-9- yl)ethyl)phosphonate (292 mg, 0.5 mmol, 1.0 equivalent), (E)-(l-cyano-2-(2,5- dibromophenyl)vinyl) diethyl phosphate (210 mg, 0.5 mmol, 1.0 equivalent), tris(dibenzylideneacetone)dipalladium(0) (13 mg, 0.014 mmol, 3 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) (25 mg, 0.06 mmol, 12 mol%), and potassium phosphate (425 mg, 2.0 mmol, 4 equivalents) in 5 mL of dioxane and 2 mL of water under a N2atmosphere. The resulting mixture was refluxed under the same N2atmosphere for 15 h. The resulting mixture was extracted with CH2Cl2and the organic layer was dried over anhydrous MgSO4and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.38 (s), 8.20 (m), 7.64 (m), 4.28 (m), 2.05 (m), 1.92 (m), 1.32 (m); SEC data: Mn= 9.2 x 10 3 g mol –1 ,

[0149] CPCN:

[0150] To a solution of preCPCN (100 mg) in 20 mL of anhydrous CH2Cl2under a nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to obtain 75 mg of CPCN as a grey solid with a yield of 96%. 1 H-NMR (CDC13and CD3OD, 400 MHz) δ (ppm): 8.42 (s), 7.59 (m), 7.00 (m), 5.01 (s), 4.05 (m), 2.85 (m), 2.00 (m).

[0151] Example 4 - Synthesis of CP5CN copolymers

[0152]

[0153] Dimethyl(1-cyano-2-(2,5-dibromophenyl)butyl)phosphonate:

[0154] To a suspension of sodium hydride (60% in mineral oil, 220 mg, 5.5 mmol, 1.1 eq) in 28 mL of anhydrous DMF under a nitrogen atmosphere was added (cyanomethyl)dimethyl phosphonate (0.9 mL, 5.5 mmol, 1.1 eq) at 0 °C. The reaction mixture was stirred for 30 min. Subsequently, a solution of 1,4-dibromo-2-(4-bromobutyl)benzene (1.85 g, 5.0 mmol, 1.0 eq) in 10 mL of anhydrous DMF was added dropwise to the reaction mixture. The reaction mixture was allowed to warm to room temperature and stirred for 12 h, then quenched with water. The resulting mixture was extracted with CH2Cl2and the organic layer was washed with brine, dried over anhydrous MgSO4and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel using CH2Cl2as eluent to obtain 2.02 g (4.6 mmol) of (1-cyano-2-(2,5-dibromophenyl)butyl)dimethyl phosphonate as a light yellow oil with a yield of 92%. 1H-NMR (CDC13) δ (ppm): 7.44 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.22 (s, 2H), 3.70 (s, 6H), 3.82 (s, 6H), 2.60 (m, 2H), 1.86 (m, 2H), 2.40 (m, 1), 1.81 (m, 2H), 1.62 (m, 2H), 1.28 (m, 2H). HRMS (ESI): calcd. for C 14 H 18 Br2NO3P([M] + ): 436.9391, found: 436.9377.

[0155] preCP5CN:

[0156] To a mixture of (2-(3,6-bis(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-9H- carbazol-9-yl)ethyl)phosphonate (292 mg, 0.5 mmol, 1.0 equiv), (l-cyano-2-(2,5- dibromophenyl)butyl)dimethyl phosphonate (220 mg, 0.5 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium(0) (13 mg, 0.014 mmol, 3 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) (25 mg, 0.06 mmol, 12 mol%) and potassium phosphate (425 mg, 2.0 mmol) in 5 mL of dioxane and 2 mL of water under N2atmosphere. The resulting mixture was refluxed under the same N2atmosphere for 15 h. The resulting mixture was extracted with CH2Cl2, the organic layer was dried over anhydrous MgS04and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and was dropped into a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to obtain 250 mg of preCP5CN as a grey solid with a yield of 82%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.35 (m), 8.20 (m), 7.64 (m), 4.20 (m), 3.71 (m), 2.5 (m), 2.05 (m), 1.92 (m), 1.68 (m), 1.32 (m).; SEC data: Mn= 11.2 x 103g mol 3 g mol –1 , CP5CN:

[0157] To a solution of preCP5CN (100 mg) in 20 mL of anhydrous CH2Cl2under a nitrogen atmosphere, a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2was added dropwise. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether, and the process of repeated precipitation and filtration was performed twice to give 77 mg of CP5CN as a grey solid with a yield of 97%. 1 H-NMR (CDC13and CD3OD, 400 MHz) δ (ppm): 8.42 (m), 7.59 (m), 7.00 (m), 4.10 (m), 2.65 (m), 2.00 (m), 1.28 (m).

[0158] Example 5 - Synthesis of TT-1, TT-2, and TT-3 copolymers

[0159]

[0160] preTT-1:

[0161] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 equiv), 2,2’-bipyridine (263 mg, 1.70 mmol, 1.0 equiv), and cyclooctadiene (184 mg, 1.70 mm, 1.0 equiv) was added 25 mL of anhydrous bubbled DMF under a nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 min. Subsequently, a solution of (E)-(2-(4-(bis(4-bromophenyl)amino)phenyl)-1-cyanoethenyl)dimethyl phosphonate (286 mg, 0.51 mmol, 0.3 equiv) and N,N-bis(4-bromophenyl)-2,4,6-trimethylaniline (227 mg, 0.51 kmol, 0.3 equiv) in 8 mL of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature, and the pH was adjusted to 1-2 by the addition of 1 M HCl. The resulting mixture was extracted with CH2Cl2, and the organic layer was washed with 1 M HCl three times. The organic layer was dried over anhydrous Na2SO4and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to give 228 mg of preTT-1 as a yellow solid with a yield of 65%. 1H-NMR (CDC13, 400 MHz) δ (ppm): 7.90 (m), 7.62 (m), 7.19 (s), 6.80 (s), 4.02 (m), 2.22 (m).; SEC data: Mw= 8.2 x 103, Mn= 6.9 x 103, PD = 1.19 n = 8.2 x 103, Mn= 6.9 x 103, PD = 1.19 3 g mol –1 ,

[0162] TT-1:

[0163] To a solution of preTT-1 (100 mg) in 20 mL of anhydrous CH2Cl2under a nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h, or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether, and the process of repeated precipitation and filtration was performed twice to give 94 mg of orange solid TT-1 in 98% yield. 1 H-NMR (CDC13 and CD3OD, 400 MHz) δ (ppm): 7.85 (s), 7.57 (m), 6.90 (m), 4.90 (s), 2.60 (m).

[0164] preTT-2:

[0165] The synthetic route of preTT-2 was similar to preTT-1 except that a solution of (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)diethyl phosphonate (197 mg, 0.35 mmol, 0.21 eq) and N,N-bis(4-bromophenyl)-2,4,6-trimethylbenzenamine (312 mg, 0.70 mmol, 0.42 eq) in 8 ml of anhydrous DMF was used. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature, and the pH was adjusted to 1-2 by adding 1 M HC1. The resulting mixture was extracted with CH2Cl2, and the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2S04, and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2, and added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h, or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to give 261 mg of preTT-1 as a yellow solid in 77% yield. 1H-NMR (CDC13, 400 MHz) δ (ppm): 7.90 (m), 7.62 (m), 7.20 (s), 6.80 (s), 4.02 (m), 2.22 (m).; SEC data: Mw= 9.8 x 103, Mn= 6.2 x 103, Mw / Mn= 1.58 n = 9.8 x 10 3 g mol –1 , TT-2:

[0166] The synthetic route of TT-2 is similar to TT-1 except using a solution of preTT-2 (100 mg) in 20 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with ether, and the precipitation and filtration were repeated twice to give 94 mg of TT-2 as an orange solid with a yield of 97%. 1 H-NMR (CDC13 and CD3OD, 400 MHz) δ (ppm): 7.86 (s), 7.57 (m), 6.90 (m), 4.90 (s), 2.60 (m).

[0167] preTT-3:

[0168] The synthetic route of preTT-3 is similar to preTT-1 except using a solution of (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)diethyl phosphonate (151 mg, 0.27 mmol, 0.16 eq) and N,N-bis(4-bromophenyl)-2,4,6-trimethylaniline (356 mg, 0.80 mmol, 0.47 eq) in 6 ml of anhydrous DMF. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature, and the pH was adjusted to 1-2 by adding 1 M HC1. The resulting mixture was extracted with CH2Cl2, and the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2S04and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with ether to give 244 mg of preTT-3 as a yellow solid with a yield of 72%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.90 (m), 7.62 (m), 7.20 (s), 6.80 (s), 4.02 (m), 2.22 (m).; SEC data: Mw= 9.8 x 103, Mn= 6.2 x 103, Mw / Mn= 1.58 n = 10.2 x 103 g mol –1 , TT-3:

[0169] The synthesis route of TT-3 is similar to TT-1 except using a solution of preTT-3 (100 mg) in 20 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether, and the precipitation and filtration were repeated twice to obtain 91 mg of TT-3 as an orange solid with a yield of 93%. 1 H-NMR (CDC13and CD3OD, 400 MHz) δ (ppm): 7.86 (s), 7.60 (m), 6.92 (m), 4.90 (s), 2.60 (m).

[0170] Example 6 - Synthesis of CC1 copolymers

[0171]

[0172] preCC-1:

[0173] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 equiv), 2,2’-bipyridine (263 mg, 1.70 mmol, 1.0 equiv) and cyclooctadiene (184 mg, 1.70 mm, 1.0 equiv) was added 25 mL of anhydrous bubbled DMF under a nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 min. Subsequently, a solution of diethyl (4-(3,6-dibromo-9H-carbazol-9-yl)butyl)phosphonate (264 mg, 0.51 mmol, 0.3 equiv) and (2-(3,6-dibromo-9H-carbazol-9-yl)ethyl)phosphonate (249 mg, 0.51 mm, 0.3 equiv) in 6 mL of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature and the pH was adjusted to 1-2 by adding 1 M HC1. The resulting mixture was extracted with CH2Cl2and the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2S04and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to obtain 193 mg (60%) of preCC-1 as a grey solid with a yield of 55%. 1H-NMR (CDC13, 400 MHz) δ (ppm): 8.78 (m), 7.80 (m), 4.10 (m), 4.02 (m), 2.00 (m), 1.28 (m).; SEC data: Mw= 13.2 x 103, Mn= 6.6 x 103, Mw / Mn= 2.0. n = 13.2 x 103 3 gmol –1 ,

[0174] CC-1:

[0175] To a solution of pre-CC-1 (120 mg) in 10 mL of anhydrous CH2Cl2under a nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether, and the precipitation and filtration were repeated twice to give 85 mg of white solid CC-1 with a yield of 85%. 1 H-NMR (CDC13 and CD3OD, 400 MHz) δ (ppm): 8.78 (m), 7.80 (m), 4.92 (m), 4.00 (s), 1.98 (m), 1.29 (m).

[0176] Example 7 - Synthesis of 5-PACz-CN

[0177]

[0178] Dimethyl(1-cyano-5-(3,6-dibromo-9H-carbazol-9-yl)pentyl)phosphonate:

[0179] To a suspension of sodium hydride (60% in mineral oil, 220 mg, 5.5 mmol, 1.1 eq) in 28 mL of anhydrous DMF was added (cyanomethyl)dimethyl phosphonate (0.9 mL, 5.5 mmol, 1.1 eq) at 0 °C under nitrogen atmosphere. The reaction mixture was stirred for 30 min. Subsequently, a solution of 3,6-dibromo-9-(4-bromobutyl)-9H-carbazole (2.30 g, 5.0 mmol, 1.0 eq) in 10 mL of anhydrous DMF was added dropwise to the reaction mixture. The reaction mixture was allowed to warm to room temperature and stirred for 12 h, then quenched with water. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel with CH2Cl2as eluent to give 1.85 g (3.5 mmol) of (1-cyano-5-(3,6-dibromo-9H-carbazol-9-yl)pentyl)dimethyl phosphonate as a blue solid in 70% yield. 13 C-NMR (CDCI3) δ (ppm): 134.0, 126.1, 124.7, 123.5, 122.7, 117.2, 117.2, 58.2, 52.1, 31.9, 28.2, 25.9, 14.1. HRMS (ESI): calcd. for C 20 H 21 Br2N2O3P ([M] + ): 525.9657, found: 525.9633.

[0180] 5-PECz-CN:

[0181] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 eq), 2,2'-bipyridine (263 mg, 1.70 mmol, 1.0 eq) and cyclooctadiene (184 mg, 1.70 mm, 1.0 eq) was added 25 mL of anhydrous degassed DMF under nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 min. Subsequently, (1-cyano-5-(3,6-dibromo-9H-carbazol-9-yl)pentyl)dimethyl phosphonate (560 mg, 1.06 mmol, 0.62 eq) dissolved in 6 mL of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 h. It was allowed to cool to room temperature, 1 M HC1 was added to adjust the pH to 1-2. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2SO4and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h, or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to give 195 mg of 5-PECz-CN as a grey solid in 50% yield.1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.88 (m), 7.52 (m), 4.10 (m), 3.67 (m), 2.48 (s), 1.88 (m), 1.60 (m), 1.30 (m); SEC data: Mw= 12.2 x 10 n 3 g mol –1

[0182] 5-PACz-CN:

[0183] To a solution of 5-PECz-CN (100 mg) in 18 mL of anhydrous CH2Cl2under nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to give 83 mg of 5-PACz-CN as a white solid with a yield of 90%. 1 H-NMR (CDC13 and CD3OD, 400 MHz) δ (ppm): 7.78 (m), 7.42 (m), 4.88 (m), 4.22 (s), 2.42 (s), 1.88 (m), 1.60 (m), 1.30 (m).

[0184] Example 8 - Synthesis of 2-PACz-m

[0185]

[0186] 2,7-dibromo-9-(2-bromoethyl)-9H-carbazole:

[0187] ​​To a mixture of 2,7-dibromo-9H-carbazole (3.25 g, 10 mmol, 1.0 equiv), 1,2-dibromoethane (1.3 mL, 15 mmol, 1.5 equiv), sodium hydroxide (1.6 g, 40 mmol, 4.0 equiv) and tetrabutylammonium bromide (0.97 g, 3 mmol, 30 mol%) was added 50 mL THF and 20 mL water. The reaction mixture was stirred at 40 °C for 12 h. The resulting mixture was extracted with ethyl acetate, the organic layer was washed with brine, dried over anhydrous MgS04and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using hexane / CH2Cl24 / 1 (v / v) as eluent to give 3.9 g (9 mmol) of 2,7-dibromo-9-(2-bromoethyl)-9H-carbazole as a white solid in 90% yield. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.62 (s, 2H), 8.23 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 4.35 (t, J = 8.0 Hz, 2H), 3.62 (t, J = 8.0 Hz, 2H. 13 C-NMR (CDC13, 100 MHz) δ (ppm): 131.9, 126.2, 123.1, 117.9, 114.2, 112.2, 62.2, 31.9. HRMS (ESI): calcd. for C 14 H 10 Br3N([M] + ): 428.8363, found: 428.8300.

[0188] Diethyl(2-(2,7-dibromo-9H-carbazol-9-yl)ethyl)phosphonate:

[0189] To a mixture of 2,7-dibromo-9-(2-bromoethyl)-9H-carbazole (500 mg, 1.16 mmol) was added 5 mL of triethyl phosphite under nitrogen atmosphere. The reaction mixture was stirred at 150 °C for 15 h. The resulting mixture was concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate as eluent to give 498 mg (1.02 mmol) of (2-(2,7-dibromo-9H-carbazol-9-yl)ethyl) diethyl phosphonate as a light yellow oil in 88% yield. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.61 (s, 2H), 8.13 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 4.20 (m, 4H), 4.10 (t, J = 8.0 Hz, 2H), 2.00 (m, 2H), 1.36 (m, 6H).13 C-NMR (CDC13, 100 MHz) δ (ppm): 131.9, 126.3, 123.2, 117.9, 114.2, 112.2, 62.9, 44.1, 31.2, 16.1. HRMS (ESI): calcd. for C 18 H 20 Br2NO3P ([M] + ): 486.9548, found: 486.9542.

[0190] 2-PECz-m:

[0191] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 eq), 2,2’-bipyridine (263 mg, 1.70 mmol, 1.0 eq) and cyclooctadiene (184 mg, 1.70 mm, 1.0 eq) was added 25 mL of anhydrous degassed DMF under nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 min. The reaction mixture was stirred at 80 °C for 60 min. Subsequently, diethyl (2-(2,7-dibromo-9H-carbazol-9-yl)ethyl)phosphonate (498 mg, 1.02 mmol, 0.6 eq) dissolved in 6 ml of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature, 1 M HC1 was added to adjust the pH to 1-2. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2 and was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to give 202 mg of 2-PECz-m as a grey solid in 58% yield. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 8.22 (m), 7.85 (m), 7.66 (m), 4.23 (m), 2.00 (m), 1.30 (m).; SEC data: M n = 12.8 x 10 3 g mol –1 ,

[0192] 2-PACz-m:

[0193] To a solution of 2-PECz-m (100 mg) in 15 mL of anhydrous CH2Cl2under nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until the precipitation was formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to give 75 mg of white solid 2-PACz-m with a yield of 90%. 1 H-NMR (CDC13 and CD3OD, 400 MHz) δ (ppm): 8.22 (m), 7.80 (m), 7.60 (m), 4.80 (m), 4.12 (m), 2.00 (m).

[0194] Example 9 - Synthesis of homopolymer 4-PAOCz

[0195]

[0196] 2,7-dimethoxy-9H-carbazole:

[0197] To a solution of 2,7-dibromo-9H-carbazole (3.25 g, 10 mmol, 1 equiv) and sodium methoxide (5.6 mL, 5.4 M in methanol, 30 mmol, 3 equiv) in 12 mL of anhydrous DMF at room temperature was added copper(I) iodide (380.9 mg, 2 mmol, 20 mol %). The reaction mixture was stirred at 110 °C for 60 min. It was cooled to room temperature and then quenched with water. The resulting mixture was extracted with CH2Cl2, and the organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with CH2Cl2as eluent to give 1.82 g (8 mmol) of white solid 2,7-dimethoxy-9H-carbazole with a yield of 80%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 10.1 (s, 1H), 7.63 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 7.02 (s, 2H), 3.87 (s, 6H). 13 C-NMR (CDC13, 100 MHz) δ (ppm): 156.7, 136.5, 128.3, 121.7, 109.2, 95.0, 55.3. HRMS (ESI): calcd. for C 22 H 24Br2N2([M] + ):227.0946,found:227.0983.

[0198] 3,6-dibromo-2,7-dimethoxy-9H-carbazole:

[0199] Under ice bath conditions, 15 mL of anhydrous DMF solution of N-bromosuccinimide (3.56 g, 20 mmol, 2 equivalents) was added to 15 mL of anhydrous DMF solution of 2,7-dimethoxy-9H-carbazole (2.27 g, 10 mmol, 1 equivalent). The reaction mixture was stirred at 0 °C for 2 hours. It was then heated to room temperature and quenched with water. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using CH2Cl2 as the eluent to give 3.47 g (9 mmol) of white solid 3,6-dibromo-2,7-dimethoxy-9H-carbazole in 90% yield. 1 H-NMR (CDCl3, 400MHz) δ (ppm): 10.1 (s, 1H), 8.07 (s, 2H), 6.90 (s, 2H), 4.00 (s, 6H). 13 C-NMR(CDCl3,100MHz)δ(ppm):149.7,136.3,122.3,108.2,106.3,97.0,55.3.HRMS(ESI):calcd.forC 22 H 24 Br2N2([M] + ):384.9136,found:385.0054.3,6-dibromo-9-(4-bromobutyl)-2,7-dimethoxy-9H-carbazole:

[0200] To a mixture of 3,6-dibromo-2,7-dimethoxy-9H-carbazole (3.85 g, 10 mmol, 1.0 equiv), 1,2-dibromo butane (1.8 mL, 15 mmol, 1.5 equiv), sodium hydroxide (1.6 g, 40 mmol, 4.0 equiv) and tetrabutylammonium bromide (0.97 g, 3 mmol, 30 mol%) was added 50 mL THF and 20 mL water. The reaction mixture was stirred at 40 °C for 12 h. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using hexane / CH2Cl24 / 1 (v / v) as eluent to give 4.68 g (9 mmol) of 3,6-dibromo-9-(4-bromobutyl)-2,7-dimethoxy-9H-carbazole as a white solid in 90% yield. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.53 (s, 2H), 6.80 (s, 2H), 4.18 (m, 2H), 4.00 (s, 6H), 3.42 (m, 2H), 1.84 (m, 2H), 1.74 (m, 2H). 13 C-NMR (CDC13, 100 MHz) δ (ppm): 149.5, 130.3, 122.0, 113.3, 108.2, 97.4, 55.1, 57.3, 33.4, 30.2, 28.8. HRMS (ESI): calcd. for C 22 H 24 Br2N2([M] + ): 518.8867, found: 518.8904.

[0201] Diethyl(4-(3,6-dibromo-2,7-dimethoxy-9H-carbazol-9-yl)butyl)phosphonate:

[0202] To 3,6-dibromo-9-(4-bromobutyl)-2,7-dimethoxy-9H-carbazole (603 mg, 1.16 mmol) was added 5 mL of triethyl phosphite under nitrogen atmosphere. The reaction mixture was stirred at 150 °C for 15 h. The resulting mixture was concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate as eluent to give 536 mg (0.93 mmol) of (4-(3,6-dibromo-2,7-dimethoxy-9H-carbazol-9-yl)butyl) diethyl phosphonate as a light yellow oil in 80% yield. 1H-NMR (CDC13, 400 MHz) δ (ppm): 7.52 (s, 2H), 6.79 (s, 2H), 4.18 (m, 6H), 4.00 (s, 6H), 1.76 (m, 4H), 1.36 (m, 6H), 1.25 (m, 2H). 13 C-NMR (CDC13, 100 MHz) δ (ppm): 149.8, 130.5, 122.3, 108.0, 97.4, 62.4, 58.0, 55.3, 31.8, 31.6, 16.3, 12.8. HRMS (ESI): calcd. for C 22 H 24 Br2N2([M] + ): 577.0051, found: 577.0072.

[0203] 4-PEOCz:

[0204] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 equiv), 2,2'-bipyridine (263 mg, 1.70 mmol, 1.0 equiv) and cyclooctadiene (184 mg, 1.70 mm, 1.0 equiv) was added 25 mL of anhydrous degassed DMF under nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 minutes. The reaction mixture was stirred at 80 °C for 60 minutes. Subsequently, diethyl (4-(3,6-dibromo-2,7-dimethoxy-9H-carbazol-9-yl)butyl)phosphonate (589 mg, 1.02 mmol, 0.6 equiv) dissolved in 6 ml of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 hours. It was cooled to room temperature, 1 M HC1 was added to adjust the pH to 1-2. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2S04and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 hours or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to obtain 255 mg of 4-PEOCz as a grey solid with a yield of 60%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.36 (m), 6.90 (m), 4.21 (m), 3.79 (m), 1.80 (m), 1.40 (m).; SEC data: M n = 7.2 x 10 3 g mol –1 ,

[0205] 4-PAOCz:

[0206] To a solution of 4-PEOCz (100 mg) in 15 mL of anhydrous CH2Cl2under nitrogen atmosphere, a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2was added dropwise. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to give 78 mg of 4-PAOCz as a grey solid with a yield of 90%. 1 H-NMR (CDC13 and CD3OD, 400 MHz) δ (ppm): 7.38 (m), 6.85 (m), 4.18 (m), 3.87 (m), 1.75 (m), 1.66 (m), 1.30 (m).

[0207] Example 10 - Synthesis of homopolymer 4-PAOCz-m

[0208]

[0209] 2,7-dibromo-9-(4-bromobutyl)-3,6-dimethoxy-9H-carbazole:

[0210] To a mixture of 2,7-dibromo-3,6-dimethoxy-9H-carbazole (3.85 g, 10 mmol, 1.0 equiv), 1,2-dibromo butane (1.8 mL, 15 mmol, 1.5 equiv), sodium hydroxide (1.6 g, 40 mmol, 4.0 equiv) and tetrabutylammonium bromide (0.97 g, 3 mmol, 30 mol%) was added 50 mL of THF and 20 mL of water. The reaction mixture was stirred at 40 °C for 12 h. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography with hexane / CH2Cl24 / 1 (v / v) as eluent to give 4.68 g (9 mmol) of 2,7-dibromo-9-(4-bromobutyl)-3,6-dimethoxy-9H-carbazole as a white solid with a yield of 90%. 1 H-NMR (CDC13, 400 MHz) δ (ppm):, 7.63 (s, 2H), 7.41 (s, 2H), 4.16 (m, 2H), 4.68 (s, 6H), 3.44 (m, 2H), 1.82 (m, 2H), 1.76 (m, 2H). 13C-NMR (CDC13, 100 MHz) δ (ppm): 151.6, 128.0, 115.3, 109.2, 106.5, 104.8, 57.8, 55.2, 30.5, 28.6. HRMS (ESI): calcd. for C 22 H 24 Br2N2([M] + ): 518.8867, found: 518.8893.

[0211] Diethyl(4-(2,7-dibromo-3,6-dimethoxy-9H-carbazol-9-yl)butyl)phosphonate:

[0212] To 2,7-dibromo-9-(4-bromobutyl)-3,6-dimethoxy-9H-carbazole (603 mg, 1.16 mmol) was added 5 mL of triethyl phosphite under nitrogen atmosphere. The reaction mixture was stirred at 150 °C for 15 hours. The resulting mixture was concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate as eluent to give 536 mg (0.93 mmol) of (4-(2,7-dibromo-3,6-dimethoxy-9H-carbazol-9-yl)butyl) diethyl phosphonate as a light yellow oil in 80% yield. 1 H-NMR (CDC13, 400 MHz) δ (ppm):, 7.48 (s, 2H), 7.37 (s, 2H), 4.18 (m, 6H), 3.68 (s, 6H), 1.74 (m, 4H), 1.38 (m, 6H), 1.24 (m, 2H). 13 C-NMR (CDC13, 100 MHz) δ (ppm): 151.8, 128.3, 115.7, 109.6, 106.3, 104.1, 62.8, 58.0, 55.7, 31.5, 31.0, 16.8, 12.5. HRMS (ESI): calcd. for C 22 H 24 Br2N2([M] + ): 577.0051, found: 577.0109.

[0213] 4-PEOCz-m:

[0214] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 eq), 2,2’-bipyridine (263 mg, 1.70 mmol, 1.0 eq) and cyclooctadiene (184 mg, 1.70 mm, 1.0 eq) was added 25 mL of anhydrous degassed DMF under nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 min. The reaction mixture was stirred at 80 °C for 60 min. Subsequently, diethyl (4-(2,7-dibromo-3,6-dimethoxy-9H-carbazol-9-yl)butyl)phosphonate (589 mg, 1.02 mmol, 0.6 eq) dissolved in 6 ml of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature, pH was adjusted to 1-2 by adding 1 M HC1. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2S04and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to obtain 255 mg of 4-PEOCz-m as a grey solid with a yield of 60%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.76 (m), 7.29 (m), 4.19 (m), 3.82 (m), 1.76 (m), 1.35 (m); SEC data: Mw= 8.9 x 104, Mn= 6.9 x 104, PD = 1.28 n = 8.9 x 104 3 g mol –1 ,

[0215] 4-PAOCz-m:

[0216] To a solution of 4-PEOCz-m (100 mg) in 15 mL of anhydrous CH2Cl2was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2under nitrogen atmosphere. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH, the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether, repeated precipitation and filtration were performed twice to obtain 78 mg of 4-PAOCz-m as a grey solid with a yield of 90%. 1H-NMR (CDC13, 400 MHz) δ (ppm): 7.12 (m), 4.20 (m), 4.00 (m), 1.80 (m), 1.51 (m); SEC data: Mw= 8.6 x 105, Mn= 4.6 x 104, Mw / Mn= 18.5, Mz= 1.3 x 105, PD = 19.5.

[0217] Example 11 - Synthesis of homopolymer 4-PAAd

[0218]

[0219] 4-PEAd:

[0220] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 eq), 2,2’-bipyridine (263 mg, 1.70 mmol, 1.0 eq) and cyclooctadiene (184 mg, 1.70 mm, 1.0 eq) was added 25 mL of anhydrous degassed DMF under nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 min. Subsequently, diethyl (4-(2,7-dibromo-9,9-dimethyl- acridin-10(9H)-yl)butyl)phosphonate (593 mg, 1.06 mmol, 0.62 eq) dissolved in 10 mL of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 h. It was cooled to room temperature, pH was adjusted to 1-2 by addition of 1 M HC1. The resulting mixture was extracted with CH2Cl2, the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2 and was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until the precipitation was formed. The resulting polymer was filtered and washed with diethyl ether to give 190 mg of white solid 4-PEAd with 45% yield. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.12 (m), 4.20 (m), 4.00 (m), 1.80 (m), 1.51 (m); SEC data: Mw= 8.6 x 105, Mn= 4.6 x 104, Mw / Mn= 18.5, Mz= 1.3 x 105, PD = 19.5. n = 8.6 x 105 3 g mol –1 ,

[0221] 4-PAAd:

[0222] To a solution of 4-PEAd (60 mg) in 15 mL of anhydrous CH2Cl2under a nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to give 44 mg of 4-PAAd as a white solid with a yield of 85%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.08 (m), 4.20 (m), 3.95 (m), 1.80 (m), 1.51 (m); SEC data: Mw= 6.8 x 105, Mn= 3.4 x 105, PD = 2.0.

[0223] Example 12 - Synthesis of homopolymer 4-PAPOZ

[0224]

[0225] 4-PEPOZ:

[0226] The synthesis route of 4-PEPOZ was similar to that of 4-PEAs, except that (4-(3,7-dibromo-10H-phenoxazin-10-yl)butyl)phosphonic acid diethyl ester (565 mg, 1.06 mmol) was used instead of (4-(2,7-dibromo-9,9-dimethylacridin-10(9H)-yl)butyl)phosphonic acid diethyl ester. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered and washed with diethyl ether to give 154 mg of 4-PEPOZ as a grey solid with a yield of 39%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.08 (m), 4.20 (m), 3.95 (m), 1.80 (m), 1.51 (m); SEC data: Mw= 6.8 x 105, Mn= 3.4 x 105, PD = 2.0. n = 6.8 x 105 3 g mol –1 ,

[0227] 4-PAPOZ:

[0228] The synthetic route of 4-PAPOZ was similar to that of 4-PAAd, except that 60 mg of 4-PEPOZ was used. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was re-dissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of ether for 1-2 h, or until a precipitate formed. The resulting polymer was filtered and washed with ether, and the precipitation and filtration were repeated twice to give 44 mg of 4-PAPOZ as a white solid with a yield of 86%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.15 (m), 4.20 (m), 3.98 (m), 1.80 (m), 1.51 (m); SEC data: Mw= 9.8 x 103, Mn= 8.6 x 103, Mw / Mn= 1.14, PDI = 1.14.

[0229] Example 13 - Synthesis of homopolymer 4-PAPTZ

[0230]

[0231] 4-PEPTZ:

[0232] The synthetic route of 4-PEPTZ was similar to that of 4-PEAs, except that (4-(3,7-dibromo-10H-phenothiazin-10-yl)butyl)phosphonic acid diethyl ester (582 mg, 1.06 mmol) was used instead of (4-(2,7-dibromo-9,9-dimethylacridin-10(9H)-yl)butyl)phosphonic acid diethyl ester. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of ether for 1-2 h, or until a precipitate formed. The resulting polymer was filtered and washed with ether to give 194 mg of 4-PEPOZ as a white solid with a yield of 47%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.15 (m), 4.20 (m), 3.98 (m), 1.80 (m), 1.51 (m); SEC data: Mw= 9.8 x 103, Mn= 8.6 x 103, Mw / Mn= 1.14, PDI = 1.14. n = 9.8 x 103, Mn= 8.6 x 103, Mw / Mn= 1.14, PDI = 1.14. 3 g mol –1 ,

[0233] 4-PAPTZ:

[0234] The synthesis route of 4-PAPTZ was similar to that of 4-PAAd except that 60 mg of 4-PEPTZ was used. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 hours. The crude mixture was concentrated under reduced pressure. The residue was re-dissolved in a minimum amount of CH2Cl2and MeOH and the resulting solution was added dropwise to a vigorously stirred solution of ether for 1-2 hours or until a precipitate formed. The resulting polymer was filtered and washed with ether, and the precipitation and filtration were repeated twice to obtain 46 mg of 4-PAPTZ as a white solid with a yield of 90%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.20 (m), 4.21 (m), 4.00 (m), 1.75 (m), 1.49 (m); SEC data: Mw= 8.8 x 104, Mn= 6.9 x 104, PD = 1.27. Example 14 - Synthesis of homopolymer 4-PAPSZ

[0235]

[0236] 4-PEPSZ:

[0237] The synthesis route of 4-PEPSZ was similar to that of 4-PEAs except that (4-(3,7-dibromo-10H-phenothiazin-10-yl)butyl)phosphonic acid diethyl ester (632 mg, 1.06 mmol) was used instead of (4-(2,7-dibromo-9,9-dimethylacridin-10(9H)-yl)butyl)phosphonic acid diethyl ester. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of ether for 1-2 hours or until a precipitate formed. The resulting polymer was filtered and washed with ether to obtain 190 mg of 4-PEPSZ as a grey solid with a yield of 41%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.20 (m), 4.21 (m), 4.00 (m), 1.75 (m), 1.49 (m); SEC data: Mw= 8.8 x 104, Mn= 6.9 x 104, PD = 1.27. n = 8.8 x 104, Mn= 6.9 x 104, PD = 1.27. 3 g mol –1 ,

[0238] 4-PAPSZ:

[0239] The synthesis route of 4-PAPSZ is similar to 4-PAAd except that 60 mg of 4-PEPSZ was used. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 hours. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH and the resulting solution was added dropwise to a vigorously stirred solution of ether for 1-2 hours or until a precipitate formed. The resulting polymer was filtered and washed with ether, and the precipitation and filtration were repeated twice to obtain 42 mg of 4-PAPSZ as a white solid with a yield of 80%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.18 (m), 4.20 (m), 2.81 (m), 2.07 (m), 1.37 (m); SEC data: Mw= 5.3 x 105, Mn= 2.6 x 105, PD = 2.0.

[0240] Example 15 - Synthesis of homopolymer 2-PPA

[0241]

[0242] 2-PPE:

[0243] To a mixture of Ni(COD)2(470 mg, 1.70 mmol, 1.0 equiv), 2,2’-bipyridine (263 mg, 1.70 mmol, 1.0 equiv), and cyclooctadiene (184 mg, 1.70 mm, 1.0 equiv) was added 25 mL of anhydrous bubbled DMF under a nitrogen atmosphere. The reaction mixture was stirred at 80 °C for 60 minutes. The reaction mixture was stirred at 80 °C for 60 minutes. Subsequently, tetraethyl ((2,5-dibromo-1,4-phenylene)bis(ethane-2,1- diyl))bis(phosphonate) (575 mg, 1.02 mmol, 0.6 equiv) dissolved in 6 ml of anhydrous DMF was added dropwise to the reaction mixture. The resulting mixture was stirred at 80 °C for 18 hours. It was cooled to room temperature and the pH was adjusted to 1-2 with 1 M HC1. The resulting mixture was extracted with CH2Cl2and the organic layer was washed with 1 M HC1 three times. The organic layer was dried over anhydrous Na2S04and concentrated under reduced pressure. The crude product was dissolved in a minimum amount of CH2Cl2and added dropwise to a vigorously stirred solution of ether for 1-2 hours or until a precipitate formed. The resulting polymer was filtered and washed with ether to obtain 255 mg of 2-PPE as a grey solid with a yield of 60%. 1 H-NMR (CDC13, 400 MHz) δ (ppm): 7.18 (m), 4.20 (m), 2.81 (m), 2.07 (m), 1.37 (m); SEC data: Mw= 5.3 x 105, Mn= 2.6 x 105, PD = 2.0. n = 5.3 x 105 3 g mol –1 ,

[0244] 2-PPA:

[0245] To a solution of 2-PPE (100 mg) in 15 mL of anhydrous CH2Cl2under a nitrogen atmosphere was added dropwise a solution of bromotrimethylsilane (0.2 mL, 1.5 mmol) in 1 mL of anhydrous CH2Cl2. The reaction mixture was kept at 25 °C for 18 h. The resulting mixture was quenched with 8 mL of MeOH and the reaction mixture was stirred at room temperature for 12 h. The crude mixture was concentrated under reduced pressure. The residue was redissolved in a minimum amount of CH2Cl2and MeOH, and the resulting solution was added dropwise to a vigorously stirred solution of diethyl ether for 1-2 h or until a precipitate formed. The resulting polymer was filtered, washed with diethyl ether, and the precipitation and filtration were repeated twice to give 78 mg of 2-PPA as a grey solid with a yield of 90%. 1 H-NMR (CDC13 and CD3OD, 400 MHz) δ (ppm): 7.20 (m), 2.85 (m), 2.0 (m).

[0246] Example 16 - Device performance based on CPCN

[0247] PSCs with p-i-n structure were fabricated using a planar heterojunction structure of glass / ITO / CPCN (hole transport material) / MA0.7FA0.3PbI3(1000 nm thick) / C60 / bathocuproine (BCP) / copper (Cu). Both the HTM and perovskite layers were processed by blade coating under ambient conditions. The best PSC based on Poly-CPCN had a PCE of 26.1%, an open-circuit voltage of 1.23 V, a short-circuit current density of 25.6 mA cm-2, and a fill factor (FF) of 0.83. The best cell based on CPCN was further held at a fixed bias of 1.05 V or the maximum power point (MPP) and recorded a stable power output for 300 s. The current density was stabilized at 24.5 mA cm-2, which corresponds to a stable PCE of 25.7%. -2

[0248] By connecting the CPCN-based encapsulated PSC to an automated MPP tracker in air, a simulated 100 mW cm-2 -2 Its operational stability was monitored under AM 1.5G solar illumination intensity (30-50% relative humidity). No cooling or fans were used during the stability test, and the temperature of the cell was measured to be ~45 °C. The CPCN-based cell demonstrated excellent operational stability, retaining 99.7% of the initial efficiency after 1100 h of illumination, which can be extrapolated to a T80 lifetime of over 100,000 h.

[0249] ​The above examples are merely intended to illustrate the principles of the application and should not be construed as limiting the application as claimed. The above examples can be modified by a person of ordinary skill in the art without departing from the scope of the application as defined in the following claims.

Claims

1. A polymeric hole transport material comprising a copolymer based on a triarylamine monomer and a carbazole monomer, wherein the triarylamine monomer has the following main structural formula: R1 is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), cyanide (CN), vinyl, acid or a combination thereof; R2 is independently a straight-chain or branched alkyl chain, wherein one or more hydrogen (H) atoms are optionally substituted with fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or cyanide (CN); and The carbazole monomer comprises an alkyl chain directly bonded to the nitrogen atom of the carbazole structure. The alkyl chain has 1 to 11 carbon atoms and also has an X-terminus and a Y-terminus, where X is hydrogen (H) or cyanide (CN), and Y is selected from the following group:

2. The polymer hole transport material as described in claim 1, characterized in that, The carbazole monomer is selected from the following group: Where X is independently selected from hydrogen (H) or cyanide (CN); n is an integer independently selected from 0 to 10; and Y independently chooses from the following groups:

3. The polymer hole transport material as described in claim 2, characterized in that, X is hydrogen (H) and Y is 4. The polymer hole transport material as described in claim 1, characterized in that, The triarylamine monomer is selected from the following group: Where X is independently selected from hydrogen (H) or cyanide (CN); n is an integer independently selected from 0 to 10; and Y independently chooses from the following groups:

5. An inverted perovskite solar cell with a pin structure, wherein the inverted perovskite solar cell includes a hole transport layer, the hole transport layer comprising the polymer hole transport material as described in claim 1.

6. The inverted perovskite solar cell as described in claim 5, characterized in that, The inverted perovskite solar cell is a single-junction solar cell or at least one sub-cell contained in a multi-junction solar cell.

7. The inverted perovskite solar cell as described in claim 5, characterized in that, The inverted perovskite solar cell is arranged as an inverted perovskite sub-cell on a silicon heterojunction sub-cell in a tandem solar cell.

8. A polymeric hole transport material comprising a polymer based on a benzene monomer or a fluorene monomer or a combination thereof, wherein the benzene monomer or fluorene monomer is selected from the group consisting of: R is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), cyanide (CN), vinyl, acid, or a combination thereof.

9. The polymer hole transport material as described in claim 8, characterized in that, The benzene monomer is selected from the following group: Where X is independently selected from hydrogen (H) or cyanide (CN); n is an integer independently selected from 0 to 10; and Y independently chooses from the following groups:

10. The polymer hole transport material as described in claim 9, characterized in that, X is hydrogen (H) and Y is 11. The polymer hole transport material as described in claim 8, characterized in that, The benzene monomer has the following main structural formula:

12. The polymer hole transport material as described in claim 8, characterized in that, The polymer is a homopolymer or copolymer.

13. A polymeric hole transport material comprising a copolymer based on monomer I and monomer II, wherein monomer I is a benzene monomer or a fluorene monomer or a combination thereof, the benzene monomer or the fluorene monomer being selected from the group consisting of: R is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), cyanide (CN), vinyl, acid, or a combination thereof. Monomer II is a triarylamine monomer or a carbazole monomer or a combination thereof, wherein the triarylamine monomer has the following main structural formula: R1 is an alkyl chain containing hydrogen (H), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), cyanide (CN), vinyl, acid or a combination thereof; R2 is independently a straight-chain or branched alkyl chain, wherein one or more hydrogen (H) atoms are optionally substituted with fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or cyanide (CN); and The carbazole monomer comprises an alkyl chain directly bonded to the nitrogen atom of the carbazole structure. The alkyl chain has 1 to 11 carbon atoms and also has an X-terminus and a Y-terminus, where X is hydrogen (H) or cyanide (CN), and Y is selected from the following group:

14. The polymer hole transport material as described in claim 13, characterized in that, The carbazole monomer is selected from the following group: Where X is independently selected from hydrogen (H) or cyanide (CN); n is an integer independently selected from 0 to 10; and Y independently chooses from the following groups:

15. An inverted perovskite solar cell having a pin structure, wherein the inverted perovskite solar cell includes a hole transport layer, the hole transport layer comprising the polymer hole transport material as described in claim 8.

16. The inverted perovskite solar cell as described in claim 15, characterized in that, The inverted perovskite solar cell is a single-junction solar cell or at least one sub-cell contained in a multi-junction solar cell.

17. The inverted perovskite solar cell as described in claim 15, characterized in that, The inverted perovskite solar cell is arranged as a silicon heterojunction in a tandem solar cell. Inverted perovskite subcell on a (silicon heterojunction) subcell.

18. A polymeric hole transport material comprising a polymer based on a fused carbazole monomer, said fused carbazole monomer being selected from the group consisting of: Where X is independently selected from hydrogen (H) or cyanide (CN); n is an integer independently selected from 0 to 10; and Y independently chooses from the following groups:

19. The polymer hole transport material as described in claim 18, characterized in that, The polymer is a homopolymer. Substances or copolymers.

20. The polymer hole transport material as described in claim 18, characterized in that, X is hydrogen (H) and Y is 21. An inverted perovskite solar cell with a pin structure, wherein the inverted perovskite solar cell includes a hole transport layer, the hole transport layer comprising the polymer hole transport material as described in claim 18.

22. The inverted perovskite solar cell as described in claim 21, characterized in that, The inverted perovskite solar cell is a single-junction solar cell or at least one sub-cell contained in a multi-junction solar cell.

23. The inverted perovskite solar cell as described in claim 21, characterized in that, The inverted perovskite solar cell is arranged as a silicon heterojunction in a tandem solar cell. Inverted perovskite subcell on a (silicon heterojunction) subcell.

24. A polymeric hole transport material comprising a conjugated polymer having one or more repeating units, said repeating unit having at least one phosphate group [P(O)(OH)2] and at least one cyano group (C≡N) on the same side chain.

25. The polymer hole transport material as described in claim 24, characterized in that, The repeating unit is selected from the following group:

26. The polymer hole transport material as described in claim 24, characterized in that, The conjugated polymer is essentially free of triarylamine and carbazole structures.

27. An inverted perovskite solar cell having a pin structure, wherein the inverted perovskite solar cell includes a hole transport layer, the hole transport layer comprising the polymer hole transport material as described in claim 24.

28. The inverted perovskite solar cell as described in claim 27, characterized in that, The inverted perovskite solar cell is a single-junction solar cell or at least one sub-cell contained in a multi-junction solar cell.

29. The inverted perovskite solar cell as described in claim 27, characterized in that, The inverted perovskite solar cell is arranged as a silicon heterojunction in a tandem solar cell. Inverted perovskite subcell on a (silicon heterojunction) subcell.

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