WO2024243683A1

WO2024243683A1 - Ionomeric copolymers, methods, and uses thereof

Info

Publication number: WO2024243683A1
Application number: PCT/CA2024/050701
Authority: WO
Inventors: Michael Adamski; Thomas SKALSKI; Benjamin Britton; Timothy J. Peckham
Original assignee: Ionomr Innovations Inc.
Priority date: 2023-05-30
Filing date: 2024-05-27
Publication date: 2024-12-05
Also published as: KR20240171932A

Abstract

Described herein are ionomeric random, statistical, linear, branched, and block copolymers, and reinforced membranes thereof. Such ionomeric copolymers comprise both sulfonated polyphenylene monomers and non-sulfonated polyphenylene monomers. Applications of such ionomeric polymer membranes are also described herein. Such ionomeric copolymers, and membranes prepared therefrom, have applications in fuel cells, water electrolyzers, water purification, and battery products.

Description

IONOMERIC COPOLYMERS, METHODS, AND USES THEREOF CROSS-REFERENCE TO RELATED APPLICATION This application claims the benefit of U.S. Provisional Application No.63/505,012, filed May 30, 2023, the disclosure of which is hereby incorporated by reference in its entirety. BACKGROUND Sulfonated hydrocarbon-based ionomeric polymers, and proton-exchange membranes (PEMs) produced therefrom, are of increasing interest in electrochemical energy conversion devices such as fuel cells, electrolyzers, batteries, and other technology areas such as humidification and water purification devices. Among these, and in many other applications, perfluorinated materials are the dominant material used, for example, perfluorosulfonic acid (PFSA) materials such as Nafion^®. Hydrocarbon materials offer significant advantages over conventional PFSA materials including, but not limited to, improved thermomechanical stability, simplified manufacturing processes, reduced costs, and reduced environmental impacts from manufacture through to end-of-life. However, development of hydrocarbon ionomeric polymers suitable for utilization in such applications requires substantial iterative design and optimization of structure- property relationships. Ionomeric polymers should simultaneously exhibit a) high ionic conductivity; b) balanced uptake, retention, and distribution of water; c) limited swelling, volumetric expansion, and contraction behavior in response to hydration and/or dehydration, and; d) appreciable chemical robustness sufficient to withstand the dynamic electrochemical, thermochemical, and thermomechanical environments typically associated with ionomeric polymer applications. Few ionomeric polymers exhibit the necessary properties for practical use in electrochemical environments. Polymers with high degrees of functionalization (e.g., with ion exchange capacity > 2 meq/g) often uptake substantial mass (wt%) of water, and expand or swell considerably when introduced to humidity or liquid water. At the same time, reduced humidification can lead to substantial internal stress (i.e., a large force of dehydration), and reduced ionic conductivity. These effects are further exacerbated during 2296-P5WO 1 electrochemical operation (e.g., in a hydrogen fuel cell), wherein water fluxes and gradients of hydration exist both due to electroosmotic drag and the formation or consumption of water. The foregoing constitute a mechanical stress on the ionomeric polymer membrane in-situ and, without appreciable robustness, such as resistance to swelling and deformation, may result in premature failure of the ionomeric polymer membrane, leading to failure of the device in which the membrane is incorporated. Hence, methodologies to reduce the swelling behavior and/or improve mechanical resilience and toughness of ionomeric polymers, and membranes comprising ionomeric polymers, are critical in improving the general lifetime of ionomeric polymers and ionomeric polymer-containing membranes within desired applications. Typical approaches for reducing the swelling of an ionomeric polymer and ionomeric polymer-containing membranes include reduction of the ionomeric polymer ion- exchange capacity (IEC). Reducing the number of acid functional units in an ionomeric polymer decreases the material's hydrophilicity, and typically results in reduced water uptake and swelling, which is desired. However, reduced ionic (proton) conductivity and electrochemical performance also typically results, which is undesirable. The foregoing effects are typically linearly related, wherein reduction in water uptake is proportional to reduction in IEC, and decreased swelling is proportional to reduction in proton conductivity and electrochemical performance. Therefore, a need exists for ionomeric polymer membranes which exhibit sufficiently low water uptake and swelling, and which concurrently exhibit sufficient proton conductivity and electrochemical performance, for use in electrochemical environments and applications. SUMMARY This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. In some aspects, provided herein is a copolymer, comprising a first repeating unit (x) having Formula (I): 2296-P5WO 2 R_1E

a second repeating unit (y) having Formula (II):

wherein the copolymer comprises: a mole percent of (x) of about 75% to about 99%, a mole percent of (y) of about 25% to about 1%, and wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and} ^R _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each

or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-

R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{each R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{is unsubstituted or substituted with 1, 2, 3, 4, or 5} ^{substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} 2296-P5WO 3 ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, and cyano;} ^A ₁ ^{and B} ₁ ^{are independently arylene, heteroarylene, aralkylene, or} heteroaralkylene, wherein the arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{and B} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{and K} ₁ ^{are independently a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{and K} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{and K} ₃ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} X⁺ _{is a cation.} In other aspects, provided herein is a method of making a random copolymer, comprising forming a mixture of a first repeating unit (x) of Formula (VI):

(VI) wherein: 2296-P5WO 4 ^R _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, and provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^, ^{and R} _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and}

_COO-_X ⁺ _; A₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} X⁺ _{is a cation; and} A is a reactive first terminal group, and a second repeating unit (y) of Formula (VII): 2296-P5WO 5 R_3E B wherein

R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{the R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, and cyano;} ^B ₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, B₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; K₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; K₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; and B is a second reactive terminal group configured to react with A, and reacting A and B to provide a random copolymer of Formula (III): 2296-P5WO 6 R_1E R_3B y

, wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. In yet other aspects, provided herein are membranes comprising the copolymer described herein. DESCRIPTION OF THE DRAWINGS The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein: FIG.1 shows a simplified equivalent circuit. CPEdl r-is the interfacial impedance at the electrode surface, Rb is the impedance of the electrolyte membrane, and Cb is the bulk membrane capacitance. FIGs.2A and 2B shows swell (wet)/deswell (dry) cycling design of experiment. FIGs.3A – 3D show results of membrane swell/deswell tests of 100%-sPP, 90%- sPP, 80%-sPP, and 70%-sPP unreinforced membranes. FIG.4A shows water uptake of reinforced membranes containing either 100% functionalized sulfonated polyphenylenes 100%-sPP (n=15) or copolymer comprising 90% functionalized sulfonated polyphenylene and 10% non-sulfonated polyphenylene (90%- sPP) (n=30). FIG.4B shows thickness swelling of reinforced membranes containing either 100% functionalized sulfonated polyphenylenes 100%-sPP (n=15) or copolymer comprising 90% functionalized sulfonated polyphenylene and 10% non-sulfonated polyphenylene (90%- sPP) (n=30). FIG.5 shows dimensional swelling (machine direction (MD) and transverse direction (TD)) of reinforced membranes containing either 100% functionalized sulfonated 2296-P5WO 7 polyphenylenes 100%-sPP (n=15) or copolymer comprising 90% functionalized sulfonated polyphenylene and 10% non-sulfonated polyphenylene (n=30). FIG.6 shows in-plane and through-plane proton conductivity of reinforced membranes containing either 100% functionalized sulfonated polyphenylenes 100%-sPP (n=15) or copolymer comprising 90% functionalized sulfonated polyphenylene and 10% non-sulfonated polyphenylene (n=30). FIG.7 shows results of membrane swell/de-swell tests of reinforced membranes of 100%-sPP and 90%-sPP. FIG.8A shows fuel cell performance of the sPP ionomeric polymer and copolymers series and Nafion XL reinforced membranes at 80 °C, 100% RH on H₂/O₂ with 150 KPa_g backpressure. FIG.8B shows fuel cell area-specific resistance (ASR) of the sPP ionomeric polymer and copolymers series and Nafion XL reinforced membranes at 80 °C, 100% RH on H₂/O₂ with 150 KPa_g backpressure. FIG.9A shows fuel cell performance of the sPP ionomeric polymer and copolymers series and Nafion XL reinforced membranes at 80 °C, 100% RH on H2/Air with 150 KPag backpressure. FIG.9B shows fuel cell area-specific resistance (ASR) of the sPP ionomeric polymer and copolymers series and Nafion XL reinforced membranes at 80 °C, 100% RH on H2/Air with 150 KPag backpressure. FIG.10A shows fuel cell performance of sPP ionomeric polymer and copolymer series and Nafion XL reinforced membrane at 80 °C, 100% RH under H₂/Air at 300 KPa_g. FIG.10B shows fuel cell area-specific resistance (ASR) of sPP ionomeric polymer and copolymer series and Nafion XL reinforced membrane at 80 °C, 100% RH under H2/Air at 300 KPag. FIG.11A shows fuel cell performance of sPP ionomeric copolymer series and Nafion XL reinforced membrane at 80 °C, 30% RH under H₂/Air, 150 KPa_g. FIG.11B shows fuel cell area-specific resistance (ASR) of sPP ionomeric copolymer series and Nafion XL reinforced membrane at 80 °C, 30% RH under H2/Air, 150 KPag. FIG.12 shows maximum power densities (mW/cm²) measured for various MEAs comprising reinforced membranes containing either 100% functionalized sulfonated 2296-P5WO 8 polyphenylenes 100%-sPP (n=8) or copolymer comprising 90% functionalized sulfonated polyphenylene and 10% non-sulfonated polyphenylene (n=9). FIG.13 shows area-specific resistance (mΩ/cm²) measured for various MEAs comprising reinforced membranes containing either 100% functionalized sulfonated polyphenylenes 100%-sPP (n=8) or copolymer comprising 90% functionalized sulfonated polyphenylene and 10% non-sulfonated polyphenylene (n=9). DETAILED DESCRIPTION Described herein are copolymers comprising both anionic phenylene (ionomeric) and hydrophobic monomeric units, and membranes and devices comprising such compositions. The copolymers can be prepared in a convenient and well-controlled manner, with precise control of the position and number of anionic groups. Such copolymers can be used in cation exchange membranes. Definitions The term "substituted" means that an atom or group of atoms formally replaces hydrogen as a "substituent" attached to another group. The term "substituted," unless otherwise indicated, refers to any level of substitution, e.g., mono-, di-, tri-, tetra-, penta-, or higher substitution, where such substitution is permitted (e.g., results in a stable compound). The substituents are independently selected, and substitution may be at any chemically accessible position. It is to be understood that substitution at a given atom is limited by valency. A single divalent substituent, e.g., oxo, replaces two hydrogen atoms. At positions in which there is no substitution, a hydrogen atom may exist, consistent with the chemical moiety and as typically known to one in the art. For example, an aryl substituted with alkyl refers to replacement of an H atom from the aryl ring with the non- hydrogen alkyl substituent. When a group is unsubstituted, it is referred to as the group name, for example alkyl or aryl. When a group is substituted with additional functional groups, it may more generically be referred to as, e.g., substituted alkyl or substituted aryl. Substituents of compounds of the disclosure are disclosed herein in groups or in ranges. It is specifically intended that the disclosure include each and every individual subcombination of the members of such groups and ranges. For example, the terms "C_1-6 alkyl" and "C1-C6 alkyl" are specifically intended to individually disclose (without 2296-P5WO 9 limitation) methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl, whether linear or branched. For example, C4 alkyl can be n-butyl, sec-butyl, isobutyl, or tert-butyl. As an example, the term "substituted with 1, 2, 3, 4, or 5" is intended to individually disclose substitution with 1, 2, 3, or 4; 1, 2, or 3; 1 or 2; or 1 substituents. It is further intended that the compounds of the disclosure are stable. As used herein "stable" refers to a compound that is sufficiently robust to survive isolation to a useful degree of purity from a reaction mixture. It is further appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, various features of the disclosure which are, for brevity, described in the context of a single embodiment, can also be provided separately or in any suitable subcombination. It is intended that divalent groups, such as linking groups (e.g., alkylene, arylene, etc.) between a first and a second moiety, can be oriented in both a forward and a reverse direction with respect to the first and second moieties, unless specifically described otherwise. As used herein, the term "about" can be understood to include values within 10% of the stated value. For example, an IEC of about 2 meq/g means an IEC of 2 +/- 0.2 meq/g, or 1.8 – 2.2 meq/g. As used herein, the term "alkyl" refers to straight or branched hydrocarbon groups. In some embodiments, alkyl has 1 to 12 carbon atoms, alkyl has 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 1 or 2 carbon atoms, or 1 carbon atom. Representative alkyl groups include methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, sec-butyl, isobutyl, and tert-butyl), pentyl (e.g., n-pentyl, tert-pentyl, neopentyl, isopentyl, pentan-2-yl, pentan-3-yl), and hexyl (e.g., n- hexyl, geometric isomers) groups. Wherein a stereocenter occurs, alkyl refers also to any stereoisomers. As used herein, the term "alkylene" refers to a linking alkyl group. As used herein, the term "cycloalkyl" refers to non-aromatic carbocycles including cyclized alkyl, alkenyl, and alkynyl groups. Cycloalkyl groups can include mono- or polycyclic (e.g., having 2, 3 or 4) fused ring systems or spirocycles. In some embodiments, cycloalkyl groups can have from 3 to about 20 carbon atoms, 3 to about 14 carbon atoms, 2296-P5WO 10 3 to about 10 carbon atoms, or 3 to 7 carbon atoms. Cycloalkyl groups can further have 0, 1, 2, or 3 double bonds and/or 0, 1, or 2 triple bonds. Also included in the definition of cycloalkyl are moieties that have one or more aromatic rings fused (i.e., having a bond in common) to the cycloalkyl ring, for example, benzo derivatives of pentane, pentene, hexane, and the like. A cycloalkyl group having one or more fused aromatic rings is attached through non-aromatic portion. One or more ring-forming carbon atoms of a cycloalkyl group can be oxidized, for example, by having an oxo or sulfido substituent. Example cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcamyl, adamantyl, and the like. As used herein, the term "aryl" refers to an aromatic hydrocarbon group having 6 to 10 carbon atoms. Representative aryl groups include phenyl and naphthyl groups. In some embodiments, the term "aryl" includes monocyclic or polycyclic (e.g., having 2, 3, or 4 fused rings) aromatic hydrocarbons such as, for example, naphthyl, anthracenyl, indanyl, and indenyl. Also included in the definition of aryl are moieties that have one or more cycloalkyl rings fused (i.e., having a bond in common) to the aryl ring, for example, benzo derivatives of pentane, pentene, hexane, and the like. An aryl group having one or more fused cycloalkyl rings is attached though the aromatic portion. As used herein, the term "arylene" refers to a linking aryl group. For example, the term "phenylene" refers to a linking phenyl group, and “naphthylene” refers to a linking naphthyl group. As used herein, the term "aralkyl" refers to an alkyl or cycloalkyl group as defined herein, with an aryl group as defined herein, substituted for one of the alkyl hydrogen atoms. A representative aralkyl group is a benzyl group. As used herein, the term "aralkylene" refers to a linking aralkyl group. As used herein, the term "heteroaryl" refers to a 5- to 10-membered aromatic monocyclic or bicyclic ring containing 1-4 heteroatoms selected from O, S, and N. Representative 5- or 6-membered aromatic monocyclic ring groups include pyridine, pyrimidine, pyridazine, furan, thiophene, thiazole, oxazole, and isoxazole. Representative 9- or 10-membered bicyclic aromatic groups include benzofuran, benzothiophene, indole, pyranopyrrole, benzopyran, quinoline, benzocyclohexyl, and naphthyridine. As used herein, the term "heteroarylene" refers to a linking heteroaryl group. 2296-P5WO 11 As used herein, the term "heteroaralkyl" refers to an alkyl or cycloalkyl group as defined herein with a heteroaryl group as defined herein substituted for one of the alkyl hydrogen atoms. As used herein, the term "heteroaralkylene" refers to a linking heteroaralkyl group. As used herein, the term "halogen" or "halo" refers to fluoro, chloro, bromo, and iodo groups. "Halogen" or "halo" can refer to the entire set of fluoro, chloro, bromo, and iodo groups, or to a subset of halogens, e.g. fluoro, chloro, and bromo; chloro, bromo, and iodo; and any other combination or subcombination of halogen atoms. As used herein, the term "copolymer" refers to a polymer that is the result of polymerization of two or more different monomeric units. The copolymer comprises at least one monomeric unit which is ionomeric, and at least one monomeric unit which is hydrophobic. The ionomeric monomers in the copolymer can be the same or can be different. The hydrophobic monomers in the copolymer can be the same or can be different. The number and the nature of each monomeric unit can be separately controlled in a copolymer. The monomeric units can be disposed in a purely random, an alternating random, a regular alternating, a statistical, a regular block, or a random block configuration unless expressly stated to be otherwise. A purely random configuration can, for example, be: x x y z x y y z y z z z... or y z x y z y z x x.... An alternating random configuration can be: x y x z y x y z y x z…, and a regular alternating configuration can be: x y z x y z x y z…. A regular block configuration (i.e., a block copolymer) has the following example configuration when comprising 3 different monomeric units (x, y, and z) for the block: …x x x y y y z z z x x x…, while a random block configuration has the following example configurations: …x x x z z z x x x y y y y z z z x x x z z z z …., or …x-x-x-y-y-y-y-x-x-x- y-y-y-x-x-x-x-y-y-y…. A block copolymer comprises blocks of 3 or more identical monomeric units. As used herein, the term "monomeric unit" of a polymer refers to an atom or group of atoms in a polymer, comprising a part of the chain together with its pendant atoms or groups of atoms, if any, and comprises a "constitutional unit." The monomeric unit can be a repeating unit within a chain. The monomeric unit can also refer to an end group on a polymer chain. For example, the monomeric unit of polyethylene glycol can be 2296-P5WO 12 ^{– CH} ₂ ^CH ₂ ^{O– corresponding to a repeating unit, or –CH} ₂ ^CH ₂ ^{OH corresponding to an end} group. As used herein, the term "repeating unit" corresponds to the smallest monomeric unit or constitutional unit, the repetition of which constitutes a macromolecule (or oligomer molecule or block). As used herein, the term "end group" refers to a monomeric unit or constitutional unit with only one attachment to a polymer chain, located at the end of a polymer chain. For example, the end group can be derived from a monomeric unit and exists at the end of the polymer chain. As another example, the end group can be a part of a chain transfer agent or initiating agent that was used to synthesize the polymer. As used herein, the term "terminus" of a polymer refers to a monomeric unit or constitutional unit of the polymer that is positioned at the end of a polymer backbone. As used herein, the term "terminal group" refers to a functional group positioned at the end of a polymer backbone. As used herein, the term "cationic" refers to a moiety that is positively charged, or ionizable to a positively charged moiety under chemical conditions, for example by a pH lower than the pKa for the moiety. Examples of cationic moieties include, for example, ammonium, pyridinium, imino, sulfonium, quaternary phosphonium groups, etc. As used herein, the term "anionic" refers to a functional group that is negatively charged, or ionizable to a negatively charged moiety under chemical conditions, for example by a pH higher than the pKa for the moiety. Examples of anionic groups include carboxylate, sulfate, sulfonate, phosphate, phosphonate, etc. As used herein, the term "linear" refers to a polymer with a backbone which extends unilaterally, or comprises backbone atoms, functional groups, moieties, and/or monomeric units which are bound together end on end without branching. A linear polymer may not be in a straight line per se, but may be bent due to the bonding configuration (e.g. ortho- or meta- substitution of a phenyl ring) of the backbone atoms, functional groups, moieties, and/or monomeric units, or due to rotation about a bond (e.g. C-C bond) which causes the linear chain to bend or fold. A linear polymer includes a polymer comprising monomeric units which have substituents or pendent groups which may extend away from the polymer backbone. 2296-P5WO 13 As used herein, the term "branched" refers to a polymer that includes side chains or "branches" growing out from a main polymeric segment (e.g., polymer backbone). The branching is composed of similar repeating units as the main segment. A branched copolymer comprises branching monomers at a relatively low abundance in the copolymer. Branched copolymers can include a mixture of linear and branched segments. Branched ionomeric polymers are distinguished from crosslinked polymers in that a branched ionomeric polymers does not include connections between the polymeric chain(s) or pre-existing polymeric chain(s). As used herein, the term "random copolymer" is a copolymer having an irregular order or combination of the mixture of two or more monomeric units. In a purely random configuration, the monomeric units can, for example, be arranged irregularly such as in the following: …x x y z x y y z y z z z... or …y z x y z y z x x.... As used herein, the term "statistical copolymer" is a copolymer having a composition of monomeric units as determined by the mole percent of monomeric units used to generate the polymer. For example, in a statistical copolymer comprising 90% ionomeric monomer and 10% hydrophobic monomer, the resulting polymer is expected to consist of about 90% ionomeric monomer units and about 10% hydrophobic monomer units. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. Copolymers The present disclosure features, inter alia, a copolymer comprising a first repeating unit (x) having Formula (I): 2296-P5WO 14 R_1E

a second repeating unit (y) having Formula (II):

wherein the copolymer comprises: a mole percent of (x) of about 75% to about 99%, a mole percent of (y) of about 25% to about 1%, and wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and} ^R _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-

R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{the R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} 2296-P5WO 15 ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, and cyano;} ^A ₁ ^{and B} ₁ ^{are independently arylene, heteroarylene, aralkylene, or} heteroaralkylene, each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{and B} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{and K} ₁ ^{are independently a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{and K} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{and K} ₃ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} X⁺ _{is a cation.} In an embodiment, the copolymer comprises a first repeating unit (x) having Formula (I):

R_1B (I) and a second repeating unit (y) having Formula (II): 2296-P5WO 16 R_3E wherein the copolymer

a mole percent of (x) of about 75% to about 99%, a mole percent of (y) of about 25% to about 1%, and wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and} ^R _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from}

^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-_X ⁺ _; R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{the R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, and cyano;} ^A ₁ ^{and B} ₁ ^{are independently arylene, heteroarylene, aralkylene, or} heteroaralkylene, each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{and B} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; 2296-P5WO 17 ^L ₁ ^{and K} ₁ ^{are independently a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{and K} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{and K} ₃ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} X⁺ _{is a cation; and} provided that the repeating unit of Formula (I) is not:

. In some embodiments, the copolymer comprises a first repeating unit (x) having Formula (I), wherein the composition of a monomeric unit of (x) is the same as the composition of another monomeric unit of (x), or the composition of a monomeric unit of (x) is different from the composition of another monomeric unit of (x). The repeating unit (x) can be the same for all monomeric units of Formula (I) in the copolymer, or the repeating unit (x) can comprise monomeric units of (x) which are not identical. For example, (x) can differ by the number of substituents (e.g. sulfonate), or by the identity of substituents (e.g. sulfonate versus phosphonate or carbonate). 2296-P5WO 18 In some embodiments, the copolymer comprises a second repeating unit (y) having Formula (II), wherein the composition of a monomeric unit of (y) is the same as the composition of another monomeric unit of (y), or the composition of a monomeric unit of (y) is different from the composition of another monomeric unit of (y). The repeating unit (y) can be the same for all monomeric units of Formula (II) in the copolymer, or the repeating unit (y) can comprise monomeric units of y which are not identical. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% to about 99%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% to about 99%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% to about 99%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% to about 99%. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% to about 95%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% to about 95%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% to about 95%. In some embodiments, the copolymer comprises a mole percent of (x) of about 88% to about 92%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90%. In some embodiments, the copolymer comprises a mole percent of (x) of at least about 75%. In some embodiments, the copolymer comprises a mole percent of (x) of at least about 80%. In some embodiments, the copolymer comprises a mole percent of (x) of at least about 85%. In some embodiments, the copolymer comprises a mole percent of (x) of at least about 88%. In some embodiments, the copolymer comprises a mole percent of (x) of no more than about 95%. In some embodiments, the copolymer comprises a mole percent of (x) of no more than about 92%. In some embodiments, the copolymer comprises a mole percent of (y) of about 25% to about 1%. In some embodiments, the copolymer comprises a mole percent of (y) of about 20% to about 1%. In some embodiments, the copolymer comprises a mole percent of (y) of about 15% to about 1%. In some embodiments, the copolymer comprises a mole percent of (y) of about 10% to about 1%. In some embodiments, the copolymer comprises a mole percent of (y) of about 25% to about 5%. In some embodiments, the copolymer comprises a mole percent of (y) of about 20% to about 5%. In some embodiments, the copolymer comprises a mole percent of (y) of about 15% to about 5%. In some embodiments, the copolymer comprises a mole percent of (y) of about 12% to about 8%. In some 2296-P5WO 19 embodiments, the copolymer comprises a mole percent of (y) of about 10%. In some embodiments, the copolymer comprises a mole percent of (y) of about 25% or less. In some embodiments, the copolymer comprises a mole percent of (y) of about 20% or less. In some embodiments, the copolymer comprises a mole percent of (y) of about 15% or less. In some embodiments, the copolymer comprises a mole percent of (y) of about 12% or less. In some embodiments, the copolymer comprises a mole percent of (y) of at least about 5%. In some embodiments, the copolymer comprises a mole percent of (y) of at least about 8%. In some embodiments, the sum of the mole percent of the first repeating unit (x) and the mole percent of the second repeating unit (y) is about 100 mole percent. In some embodiments, the sum of the mole percent of the first repeating unit (x) and the mole percent of the second repeating unit (y) is less than about 100 mole percent. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% to about 99% and a mole percent of (y) of about 25% to about 1%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% to about 99% and a mole percent of (y) of about 25% to about 1%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% to about 99% and a mole percent of (y) of about 25% to about 1%, wherein the mole percent of x + y is less than about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% and a mole percent of (y) of about 25%. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% and a mole percent of (y) of about 25%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% and a mole percent of (y) of about 25%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 75% and a mole percent of (y) of about 25%, wherein the mole percent of x + y is less than 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% to about 99% and a mole percent of (y) of about 20% to about 1%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% to about 99% and a mole percent of (y) of about 20% to about 1%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% to about 99% and a mole percent of (y) of about 20% to about 1%, wherein the mole percent of x + y is less than about 100%. In some embodiments, the 2296-P5WO 20 copolymer comprises a mole percent of (x) of about 80% and a mole percent of (y) of about 20%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% and a mole percent of (y) of about 20%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% and a mole percent of (y) of about 20%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 80% and a mole percent of (y) of about 20%, wherein the mole percent of x + y is less than 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% to about 99% and a mole percent of (y) of about 15% to about 1%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% to about 99% and a mole percent of (y) of about 15% to about 1%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% to about 99% and a mole percent of (y) of about 15% to about 1%, wherein the mole percent of x + y is less than about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% and a mole percent of (y) of about 15%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% and a mole percent of (y) of about 15%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% and a mole percent of (y) of about 15%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 85% and a mole percent of (y) of about 15%, wherein the mole percent of x + y is less than 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% to about 99% and a mole percent of (y) of about 10% to about 1%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% to about 99% and a mole percent of (y) of about 10% to about 1%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% to about 99% and a mole percent of (y) of about 10% to about 1%, wherein the mole percent of x + y is less than about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 88% to about 92% and a mole percent of (y) of about 12% to about 8%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 88% to about 92% and a mole percent of (y) of about 12% to about 8%, wherein 2296-P5WO 21 the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 88% to about 92% and a mole percent of (y) of about 12% to about 8%, wherein the mole percent of x + y is less than about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% and a mole percent of (y) of about 10%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% and a mole percent of (y) of about 10%, wherein the mole percent of x + y is about 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% and a mole percent of (y) of about 10%, wherein the mole percent of x + y is 100%. In some embodiments, the copolymer comprises a mole percent of (x) of about 90% and a mole percent of (y) of about 10%, wherein the mole percent of x + y is less than 100%. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} ^{COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from _SO3-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} ^{COO-X+, provided that four of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO₃- _X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, and PO} ₃ ^2-X+ ₂ ^, ^{provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or} heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO₃- _X ⁺ _{, and PO3} ^2- _X ⁺ _2. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, and SO} ₃ ^{-X+, provided that at least} 2296-P5WO 22 ^{two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl substituted} _{with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} _{or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _{, provided that} ^{at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} _{substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} _{or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _{, provided that} ^{four of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl substituted} _{with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided that at least two} ^{of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl substituted with} _{1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} heteroaryl. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently _{selected from C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _, ^{provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO₃- _X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently ^{selected from C} _1-6 ^{alkyl, halo, phenyl, and SO} ₃ ^{-X+, provided that at least two of R} _1A ^{, R} _1B ^, ^R _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently heteroaryl substituted with 1, 2, 3, 4, or 5 SO} ₃- _X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO₃-X⁺, provided that at ^{least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently heteroaryl substituted} _{with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _. 2296-P5WO 23 ^{In some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO₃-X⁺, PO₃ ^2-X⁺ ₂, and COO-X⁺, provided that at least two of R_1A, R_1B, ^R _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently heteroaryl substituted with 1, 2, 3, 4, or 5} _{substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl.} ^{In some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl,} each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected _{from C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided} ^{that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl substituted} _{with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}- _X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl,} each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected _{from C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided} ^{that four of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl substituted with 1,} _{2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl,} each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected ^{from C} _1-6 ^{alkyl, halo, phenyl, and SO} ₃ ^{-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^, ^R _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl substituted with 1, 2, 3, 4, or 5 SO} ₃ ^-X+. ^{In some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl,} _{each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _{, provided that at least two of} ^R _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl substituted with 1, 2, 3, 4, or 5} _SO3-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl,} ^{each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO} ₃ ^{-X+, provided that four of R} _1A ^, ^R _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl substituted with 1, 2, 3, 4, or 5 SO} ₃- _X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl,} each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected ^{from SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^, 2296-P5WO 24 ^R _1E ^{, and R} _1F ^{are independently aryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl,} each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected _{from C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided} ^{that no more than four of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} phenyl. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently _{selected from C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _, ^{provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently _{selected from C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _, ^{provided that four of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently ^{selected from C} _1-6 ^{alkyl, halo, phenyl, and SO} ₃ ^{-X+, provided that at least two of R} _1A ^{, R} _1B ^, ^R _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl substituted with 1, 2, 3, 4, or 5 SO} ₃ ^-X+. ^{In some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO₃-X⁺, PO₃ ^2-X⁺ ₂, and COO-X⁺, provided that at least two of R_1A, R_1B, ^R _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl substituted with 1, 2, 3, 4, or 5} _{substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _. 2296-P5WO 25 ^{In some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} _{phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _{, provided that at least} ^{two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl substituted with 1, 2,} _{3, 4, or 5 SO3}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} _{phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _{, provided that four of} ^R _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl substituted with 1, 2, 3, 4, or} _{5 SO3}-_X ⁺ _. I^{n some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} ^{phenyl, each unsubstituted or substituted with SO} ₃ ^{-X+, provided that at least two of R} _1A ^, ^R _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl substituted with SO} ₃ ^-X+. ^{In some embodiments, R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently} ^{phenyl, each unsubstituted or substituted with SO} ₃ ^{-X+, provided that four of R} _1A ^{, R} _1B ^, ^R _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently phenyl substituted with SO} ₃ ^-X+. ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl} or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano.} ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently} heteroaryl. I^{n some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently} heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently ^{selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano.} ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl.} ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl,} each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected ^{from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano.} ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl,} each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected ^{from C} _1-6 ^{alkyl, halo, phenyl, nitro, and cyano.} ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently} phenyl. 2296-P5WO 26 ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently} phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently ^{selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano.} ^{In some embodiments, R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently} phenyl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently ^{selected from C} _1-6 ^{alkyl, halo, and phenyl.} ^{In some embodiments, R} _1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl,} wherein the aryl and heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^-X+, _PO3 ^2- _X ⁺ _{2, and COO}-_X ⁺ _. I^{n some embodiments, R} _1G ^{and R} _1H ^{are independently aryl, wherein the aryl are} _{each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _. I^{n some embodiments, R} _1G ^{and R} _1H ^{are independently phenyl, wherein the phenyl} _{are each unsubstituted or substituted with 1, 2, 3, 4, or 5 SO3}-_X ⁺ _. I^{n some embodiments, R} _1G ^{and R} _1H ^{are independently H.} ^{In some embodiments, R} _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl,} wherein the aryl and heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, and cyano.} ^{In some embodiments, R} _3G ^{and R} _3H ^{are independently aryl.} ^{In some embodiments, R} _3G ^{and R} _3H ^{are independently phenyl.} ^{In some embodiments, R} _3G ^{and R} _3H ^{are independently H.} ^{In some embodiments, A} ₁ ^{is arylene, heteroarylene, aralkylene, or} heteroaralkylene, unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. I^{n some embodiments, A} ₁ ^{is arylene.} ^{In some embodiments, A} ₁ ^{is arylene, unsubstituted or substituted with 1, 2, 3, or 4} substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. I^{n some embodiments, A} ₁ ^{is phenylene.} ^{In some embodiments, A} ₁ ^{is phenylene, unsubstituted or substituted with 1, 2, 3, or} 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. I^{n some embodiments, A} ₁ ^{is absent.} 2296-P5WO 27 ^{In some embodiments, B} ₁ ^{is arylene, heteroarylene, aralkylene, or} heteroaralkylene, unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. I^{n some embodiments, B} ₁ ^{is arylene.} ^{In some embodiments, B} ₁ ^{is arylene, unsubstituted or substituted with 1, 2, 3, or 4} substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. I^{n some embodiments, B} ₁ ^{is phenylene.} ^{In some embodiments, B} ₁ ^{is phenylene, unsubstituted or substituted with 1, 2, 3,} or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. I^{n some embodiments, B} ₁ ^{is absent.} ^{In some embodiments, A} ₁ ^{is phenylene, unsubstituted or substituted with 1, 2, 3, or} ^{4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl and A} ₂ is absent. I^{n some embodiments, B} ₁ ^{is phenylene, unsubstituted or substituted with 1, 2, 3, or} ^{4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl and B} ₂ is absent. I^{n some embodiments, A} ₁ ^{and B} ₁ ^{are independently arylene unsubstituted or} substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, ^{aryl, and heteroaryl, and A} ₂ ^{and B} ₂ ^{are absent.} ^{In some embodiments, L} ₁ ^{is a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₁ ^{is a linking arylene.} ^{In some embodiments, L} ₁ ^{is a linking arylene, unsubstituted or substituted with 1,} ^{2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and} heteroaryl. I^{n some embodiments, L} ₁ ^{is a linking phenylene.} ^{In some embodiments, L} ₁ ^{is a linking phenylene, unsubstituted or substituted with} ^{1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl,} and heteroaryl. I^{n some embodiments, L} ₁ ^{is a linking naphthylene.} 2296-P5WO 28 ^{In some embodiments, L} ₁ ^{is a linking naphthylene, unsubstituted or substituted with} ^{1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl,} and heteroaryl. I^{n some embodiments, L} ₁ ^{is phenylene or naphthylene. In some embodiments, L} ₁ is phenylene or naphthylene, unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₁ ^{is phenylene, provided that the phenylene is not p-} phenylene. I^{n some embodiments, L} ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₂ ^{is absent.} ^{In some embodiments, L} ₂ ^{is a linking arylene.} ^{In some embodiments, L} ₂ ^{is a linking arylene, unsubstituted or substituted with 1,} ^{2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and} heteroaryl. I^{n some embodiments, L} ₂ ^{is a linking phenylene.} ^{In some embodiments, L} ₂ ^{is a linking phenylene, unsubstituted or substituted with} ^{1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl,} and heteroaryl. I^{n some embodiments, L} ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₃ ^{is absent.} ^{In some embodiments, L} ₃ ^{is a linking arylene.} ^{In some embodiments, L} ₃ ^{is a linking arylene, unsubstituted or substituted with 1,} ^{2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and} heteroaryl. I^{n some embodiments, L} ₃ ^{is a linking phenylene.} ^{In some embodiments, L} ₃ ^{is a linking phenylene, unsubstituted or substituted with} ^{1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl,} and heteroaryl. 2296-P5WO 29 ^{In some embodiments, K} ₁ ^{is a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₁ ^{is a linking arylene.} ^{In some embodiments, K} ₁ ^{is a linking arylene, unsubstituted or substituted with 1,} ^{2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and} heteroaryl. I^{n some embodiments, K} ₁ ^{is a linking phenylene.} ^{In some embodiments, K} ₁ ^{is a linking phenylene, unsubstituted or substituted with} ^{1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl,} and heteroaryl. I^{n some embodiments, K} ₁ ^{is a linking naphthylene.} ^{In some embodiments, K} ₁ ^{is a linking naphthylene, unsubstituted or substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano,} aryl, and heteroaryl. I^{n some embodiments, K} ₁ ^{is phenylene or naphthylene. In some embodiments, K} ₁ is phenylene or naphthylene, unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₁ ^{is phenylene, provided that the phenylene is not p-} phenylene. I^{n some embodiments, K} ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₂ ^{is absent.} ^{In some embodiments, K} ₂ ^{is a linking arylene.} ^{In some embodiments, K} ₂ ^{is a linking arylene, unsubstituted or substituted with 1,} ^{2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and} heteroaryl. I^{n some embodiments, K} ₂ ^{is a linking phenylene.} 2296-P5WO 30 ^{In some embodiments, K} ₂ ^{is a linking phenylene, unsubstituted or substituted with} ^{1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl,} and heteroaryl. I^{n some embodiments, K} ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₃ ^{is absent.} ^{In some embodiments, K} ₃ ^{is a linking arylene.} ^{In some embodiments, K} ₃ ^{is a linking arylene, unsubstituted or substituted with 1,} ^{2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and} heteroaryl. I^{n some embodiments, K} ₃ ^{is a linking phenylene.} ^{In some embodiments, K} ₃ ^{is a linking phenylene, unsubstituted or substituted with} ^{1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl,} and heteroaryl. I^{n some embodiments, L} ₁ ^{and K} ₁ ^{are independently naphthylene or phenylene; L} ₂ ^{and K} ₂ ^{are independently absent or phenylene; and L} ₃ ^{and K} ₃ ^{are independently absent or} phenylene, wherein the phenylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, L} ₁ ^{and K} ₁ ^{are independently naphthylene or phenylene,} ^{provided that the phenylene is not p-phenylene; L} ₂ ^{and K} ₂ ^{are independently absent or} ^{phenylene; and L} ₃ ^{and K} ₃ ^{are independently absent or phenylene, wherein the phenylene} are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected ^{from C} _1-6 ^{alkyl and halo.} In some embodiments, the first repeating unit (x) of Formula (I) is a repeating unit of Formula (I-A):

R_1B (I-A) 2296-P5WO 31 wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from _{C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided that at} ^{least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_2A ^{, R} _2B ^{, R} _2C ^{, and R} _2D ^{are independently H, halo, nitro, cyano, aryl, or heteroaryl;} ^L ₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected ^{from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, R} _2A ^{, R} _2B ^{, R} _2C ^{, and R} _2D ^{are independently H or halo. In} ^{some embodiments, R} _2A ^{, R} _2B ^{, R} _2C ^{, and R} _2D ^{are H.} In some embodiments, the second repeating unit (y) of Formula (II) is a repeating unit of Formula (II-A):

(II-A) wherein: 2296-P5WO 32 ^R _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from ^C _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _4A ^{, R} _4B ^{, R} _4C ^{, and R} _4D ^{are independently H, halo, nitro, cyano, aryl, or heteroaryl;} ^K ₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected ^{from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} ^K ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, R4} _2A ^{, R} _4B ^{, R} _4C ^{, and R} _4D ^{are independently H or halo. In} ^{some embodiments, R} _4A ^{, R} _4B ^{, R} _4C ^{, and R} _4D ^{are H.} In some embodiments, the has a structure of Formula : y

(III), wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from _{C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided that at} ^{least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; 2296-P5WO 33 ^R _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from ^C _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^A ₁ ^{and B} ₁ ^{are independently arylene, heteroarylene, aralkylene, or} heteroaralkylene, each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{and B} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{and K} ₁ ^{are independently a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{and K} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{and K} ₃ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} X⁺ _{is a cation.} In some embodiments, the Formula (III) copolymer mole percent of the first repeating unit (x) and the second repeating unit (y) are as described herein. In some embodiments, the Formula (III) copolymer mole percent of the first repeating unit (x) is about 75% to about 99%, and the second repeating unit (y) is about 25% to about 1%. In some embodiments, the Formula (III) copolymer mole percent of the first repeating unit (x) is about 85% to about 99%, and the second repeating unit (y) is about 15% to about 1%. In some embodiments, the Formula (III) copolymer mole percent of the first repeating unit (x) is about 88% to about 92%, and the second repeating unit (y) is about 12% to about 8%. 2296-P5WO 34 In some embodiments, the Formula (III) copolymer mole percent of the first repeating unit (x) is about 75% and the second repeating unit (y) is about 25%. In some embodiments, the Formula (III) copolymer mole percent of the first repeating unit (x) is about 85% and the second repeating unit (y) is about 15%. In some embodiments, the Formula (III) copolymer mole percent of the first repeating unit (x) is about 90% and the second repeating unit (y) is about 10%. In some embodiments, the copolymer has a structure of Formula (IV): y

(IV), wherein: R_1a ^{, R} _1b ^{, R} _1e ^{, and R} _1f ^{are independently SO} ₃ ^{-X+ or hydrogen, provided that at least} ^{two of R} _1a ^{, R} _1b ^{, R} _1e ^{, and R} _1f ^{are SO} ₃ ^-X+; ^R _3a ^{, R} _3b ^{, R} _3e ^{, and R} _3f ^{are independently selected from hydrogen, C} _1-12 ^{alkyl, halo,} phenyl, nitro, and cyano; L₁ ^{and K} ₁ ^{are independently a linking arylene, unsubstituted or substituted with 1,} ^{2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and} heteroaryl; and L₂ ^{, K} ₂ ^{, L} ₃ ^{, and K} ₃ ^{are independently absent or arylene, wherein the arylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} In some embodiments, the Formula (IV) copolymer mole percent of the first repeating unit (x) and the second repeating unit (y) are as described herein. 2296-P5WO 35 In some embodiments, the Formula (IV) copolymer mole percent of the first repeating unit (x) is about 75% to about 99%, and the second repeating unit (y) is about 25% to about 1%. In some embodiments, the Formula (IV) copolymer mole percent of the first repeating unit (x) is about 85% to about 99%, and the second repeating unit (y) is about 15% to about 1%. In some embodiments, the Formula (IV) copolymer mole percent of the first repeating unit (x) is about 88% to about 92%, and the second repeating unit (y) is about 12% to about 8%. In some embodiments, the Formula (IV) copolymer mole percent of the first repeating unit (x) is about 75% and the second repeating unit (y) is about 25%. In some embodiments, the Formula (IV) copolymer mole percent of the first repeating unit (x) is about 85% and the second repeating unit (y) is about 15%. In some embodiments, the Formula (IV) copolymer mole percent of the first repeating unit (x) is about 90% and the second repeating unit (y) is about 10%. I_{n some embodiments, X} ⁺ _{is a cation selected from H} ⁺ _{, an alkali metal ion (e.g.,} _Na ⁺ _{, Li} ⁺ _{, and/or K} ⁺ _{), a transition metal ion (e.g., Fe} ²⁺ _{, Co} ²⁺ _{, Ni} ²⁺ _{, Pd} ²⁺ _{, Ir} ²⁺ _{), and} ^[N(R _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1-6 ^alkyl, aryl, or heteroaryl. I_{n some embodiments, X} ⁺ _{is a cation selected from H} ⁺ _{, an alkali metal ion (e.g.,} ^{Na+, Li+, and/or K+), and [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^are ^{independently H, C} _1-6 ^{alkyl, aryl, or heteroaryl.} I_{n some embodiments, X} ⁺ _{is H} ⁺ _. _{In some embodiments, X} ⁺ _{is an alkali metal ion (e.g., Na} ⁺ _{, Li} ⁺ _{, and/or K} ⁺ _). _{In some embodiments, X} ⁺ _{is a transition metal ion (e.g., Fe} ²⁺ _{, Co} ²⁺ _{, Ni} ²⁺ _{, Pd} ²⁺ _{, Ir} ²⁺ _). I^{n some embodiments, X+ is [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^, ^R _5D ^{are independently H, C} _1-6 ^{alkyl, aryl, or heteroaryl. In some embodiments, X+ is} ^[N(R _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H or C} _1-6 ^{alkyl. For example, X+ can be [NH(C} _1-6 ^alkyl) ₃ ^{]+. In some embodiments, X+ is} [NH(ethyl)₃]⁺. I^{n some embodiments, L} ₁ ^{is a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, 2296-P5WO 36 aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^{In some embodiments, L} ₁ ^{is unsubstituted heteroarylene. In some embodiments, L} ₁ ^{is heteroarylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₁ ^{is unsubstituted arylene. In some embodiments, L} ₁ ^is ^{arylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, L} ₁ ^{is arylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, L} ₁ ^{is unsubstituted phenylene. In some embodiments, L} ₁ ^is ^{phenylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, L} ₁ ^{is phenylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl or halo.} ^{In some embodiments, L} ₁ ^{is naphthylene.} ^{In some embodiments, L} ₁ ^{is not p-phenylene.} ^{In some embodiments, L} ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₂ ^{is absent.} ^{In some embodiments, L} ₂ ^{is unsubstituted heteroarylene. In some embodiments, L} ₂ ^{is heteroarylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₂ ^{is unsubstituted arylene. In some embodiments, L} ₂ ^is ^{arylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, L} ₂ ^{is arylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, L} ₂ ^{is unsubstituted phenylene. In some embodiments, L} ₂ ^is ^{phenylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, L} ₂ ^{is phenylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl or halo.} 2296-P5WO 37 ^{In some embodiments, L} ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, L} ₃ ^{is absent.} ^{In some embodiments, L} ₃ ^{is unsubstituted heteroarylene. In some embodiments, L} ₃ ^{is heteroarylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl. I^{n some embodiments, L} ₃ ^{is unsubstituted arylene. In some embodiments, L} ₃ ^is ^{arylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, L} ₃ ^{is arylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, L} ₃ ^{is unsubstituted phenylene. In some embodiments, L} ₃ ^is ^{phenylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, L} ₃ ^{is phenylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl or halo.} ^{In some embodiments, K} ₁ ^{is a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^{In some embodiments, K} ₁ ^{is unsubstituted heteroarylene. In some embodiments,} ^K ₁ ^{is heteroarylene substituted with 1, 2, 3, or 4 substituents independently selected from} ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₁ ^{is unsubstituted arylene. In some embodiments, K} ₁ ^is ^{arylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, K} ₁ ^{is arylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, K} ₁ ^{is unsubstituted phenylene. In some embodiments, K} ₁ ^is ^{phenylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, K} ₁ ^{is phenylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl or halo.} ^{In some embodiments, K} ₁ ^{is not p-phenylene.} 2296-P5WO 38 ^{In some embodiments, K} ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₂ ^{is absent.} ^{In some embodiments, K} ₂ ^{is heteroarylene. In some embodiments, K} ₂ ^is heteroarylene unsubstituted or substituted with 1, 2, 3, or 4 substituents independently ^{selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₂ ^{is unsubstituted arylene. In some embodiments, K} ₂ ^is ^{arylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, K} ₂ ^{is arylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, K} ₂ ^{is unsubstituted phenylene. In some embodiments, K} ₂ ^is ^{phenylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, K} ₂ ^{is phenylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl or halo.} ^{In some embodiments, K} ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₃ ^{is absent.} ^{In some embodiments, K} ₃ ^{is heteroarylene. In some embodiments, K} ₃ ^is heteroarylene unsubstituted or substituted with 1, 2, 3, or 4 substituents independently ^{selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} ^{In some embodiments, K} ₃ ^{is unsubstituted arylene. In some embodiments, K} ₃ ^is ^{arylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, K} ₃ ^{is arylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, K} ₃ ^{is unsubstituted phenylene. In some embodiments, K} ₃ ^is ^{phenylene substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^alkyl, ^{halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, K} ₃ ^{is phenylene substituted} ^{with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl or halo.} ^{In some embodiments, L} ₁ ^{and K} ₁ ^{are independently arylene; L} ₂ ^{and K} ₂ ^are ^{independently absent or arylene; and L} ₃ ^{and K} ₃ ^{are independently absent or arylene,} 2296-P5WO 39 wherein the arylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl and halo.} ^{In some embodiments, L} ₁ ^{and K} ₁ ^{are independently phenylene or naphthylene; L} ₂ ^{and K} ₂ ^{are independently absent or phenylene; and L} ₃ ^{and K} ₃ ^{are independently absent or} phenylene, wherein the phenylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _{1- 6} ^{alkyl and halo.} ^{In some embodiments, L} ₁ ^{and K} ₁ ^{are independently phenylene or naphthylene; L} ₂ ^{and K} ₂ ^{are independently absent or phenylene; and L} ₃ ^{and K} ₃ ^{are independently absent or} phenylene. I^{n some embodiments, the L} ₃ ^{, L} ₂ ^{, and L} ₁ ^{of –L} ₃ ^–L ₂ ^–L ₁ ^{–, and the K} ₃ ^{, K} ₂ ^{, and K} ₁ ^of ,

, , , 2296-P5WO 40 , In some embodiments, the first repeating unit (x) is selected from: 2296-P5WO 41 _SO ^X+ _S + 3_O3 ^X

, and any combination thereof. In some embodiments, the first repeating unit (x) is selected from: 2296-P5WO 42 _SO ^X+ _S + 3_O3 ^X + ,

, and any combination thereof.

, , 2296-P5WO 43

nd any combination thereof. In some embodiments, the second repeating unit (y) is selected from:

, , and any combination thereof, In some embodiments, the first repeating unit (x) is selected from: 2296-P5WO 44 _SO ^X+ _S + 3_O3 ^X

, _{and any combination thereof, wherein X} ⁺ _{is H} ⁺ _{, an alkali metal ion, a transition metal ion,} ^{or [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1- ₆ ^{alkyl, aryl, or heteroaryl; and}

, , 2296-P5WO 45

, and any combination thereof, wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. In some embodiments, the copolymer as described herein is a random copolymer having a random distribution of (x) and (y). In some embodiments, the copolymer as described herein is a statistical copolymer having an average composition ratio of (x) and (y). In some embodiments, the copolymer as described herein is linear. In some embodiments, the copolymer as described herein is branched. A^{branched copolymer, as described herein, comprises a multivalent linker M} ₁ ^that is directly bound through covalent bonds to at least 3 repeat units. I^{n some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to at} least 3 sulfonated polyphenylene repeat units (x) of Formula (I). In some embodiments, ^{the linker M} ₁ ^{is directly bound through covalent bonds to 3 sulfonated polyphenylene} ^{repeat units (x) of Formula (I). In some embodiments, the linker M} ₁ ^{is directly bound} through covalent bonds to 4 sulfonated polyphenylene repeat units (x) of Formula (I). In ^{some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to 5 sulfonated} ^{polyphenylene repeat units (x) of Formula (I). In some embodiments, the linker M} ₁ ^is directly bound through covalent bonds to 6 sulfonated polyphenylene repeat units (x) of ^{Formula (I). In some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds} to 3-6 sulfonated polyphenylene repeat units (x) of Formula (I). I^{n some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to at} least 3 hydrophobic polyphenylene repeat units (y) of Formula (II). In some embodiments, ^{the linker M} ₁ ^{is directly bound through covalent bonds to 3 hydrophobic polyphenylene} 2296-P5WO 46 ^{repeat units (y) of Formula (II). In some embodiments, the linker M} ₁ ^{is directly bound} through covalent bonds to 4 hydrophobic polyphenylene repeat units (y) of Formula (II). ^{In some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to 5} hydrophobic polyphenylene repeat units (y) of Formula (II). In some embodiments, the ^{linker M} ₁ ^{is directly bound through covalent bonds to 6 hydrophobic polyphenylene repeat} ^{units (y) of Formula (II). In some embodiments, the linker M} ₁ ^{is directly bound through} covalent bonds to 3-6 hydrophobic polyphenylene repeat units (y) of Formula (II). I^{n some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to at} least 3 repeat units comprising a combination of the sulfonated polyphenylene repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). I^{n some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to 3} repeat units comprising a combination of the sulfonated polyphenylene repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). For ^{example, M} ₁ ^{can be directly bound through covalent bonds to one repeat unit (x) of} Formula (I) and two repeat units (y) of Formula (II). In another example, M₁ can be directly bound through covalent bonds to two repeat units (x) of Formula (I) and one repeat unit (y) of Formula (II). I^{n some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to 4} repeat units comprising a combination of the sulfonated polyphenylene repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). For ^{example, M} ₁ ^{is directly bound through covalent bonds to one repeat unit (x) of Formula (I)} ^{and three repeat units (y) of Formula (II). In another example, M} ₁ ^{is directly bound through} covalent bonds to two repeat units (x) of Formula (I) and two repeat units (y) of Formula ^{(II). In a further example, M} ₁ ^{is directly bound through covalent bonds to three repeat units} (x) of Formula (I) and one repeat unit (y) of Formula (II). I^{n some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to 5} repeat units comprising a combination of the sulfonated polyphenylene repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). For ^{example, the linker M} ₁ ^{is directly bound through covalent bonds to 5 repeat units in any} possible combination of the repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). 2296-P5WO 47 ^{In some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to 6} repeat units comprising a combination of the sulfonated polyphenylene repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). For ^{example, the linker M} ₁ ^{is directly bound through covalent bonds to 6 repeat units in any} possible combination of the repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). I^{n some embodiments, the linker M} ₁ ^{is directly bound through covalent bonds to 3-} 6 repeat units comprising a combination of the sulfonated polyphenylene repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). For ^{example, the linker M} ₁ ^{is directly bound through covalent bonds to 3-6 repeat units in any} possible combination of the repeat units (x) of Formula (I) and the hydrophobic polyphenylene repeat units (y) of Formula (II). I^{n some embodiments, the multivalent linker M} ₁ ^{is selected from the group} consisting of: .

^. As used herein, multivalent refers to trivalent moieties and higher valency moieties ^{(e.g., tetravalent, pentavalent, hexavalent, etc.). For example, M} ₁ ^{can be a trivalent,} ^{tetravalent, pentavalent, or hexavalent linker. As an example, the multivalent linker M} ₁ ^can be a carbon atom, heteroatom (e.g., N, P, or B), multivalent aryl, multivalent heteroaryl, multivalent aralkyl, or multivalent heteroaralkyl, each of which is bound to at least 3 repeating units; wherein the carbon atom, heteroatom (e.g., P), multivalent aryl, multivalent heteroaryl, multivalent aralkyl, or multivalent heteroaralkyl are each unsubstituted or ^{substituted with 1, 2, or 3 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro,} cyano, aryl, and heteroaryl. In some embodiments, the multivalent linker is selected from trivalent nitrogen and tetravalent carbon. In some embodiments, the multivalent linker is 2296-P5WO 48 trivalent phenyl. In some embodiments, the multivalent linker is trivalent pyridyl. In some embodiments, the multivalent linker is trivalent pyrazyl. In some embodiments, the multivalent linker is tetravalent phenyl. In some embodiments, the multivalent linker is tetravalent pyridyl. In some embodiments, the multivalent linker is tetravalent pyrazyl. In some embodiments, the multivalent linker is pentavalent phenyl. In some embodiments, the multivalent linker is pentavalent pyridyl. In some embodiments, the multivalent linker is hexavalent phenyl. In embodiments comprising trivalent phenyl or trivalent pyridyl, the trivalent phenyl and trivalent pyridyl are each unsubstituted or substituted with 1, 2, or 3 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} In embodiments comprising tetravalent phenyl, tetravalent pyridyl, or trivalent pyrazyl, the tetravalent phenyl, tetravalent pyridyl, and trivalent pyrazyl, are unsubstituted or ^{substituted with 1 or 2 substituents independently selected from C} _1-6 ^{alkyl, halo, nitro,} cyano, aryl, and heteroaryl. In embodiments comprising pentavalent phenyl, the ^{pentavalent phenyl is unsubstituted or substituted with a substituent selected from C} _1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl. The multivalent linkers can be incorporated into the polymers using multi- functional aromatic systems terminated by alkynes or protected alkynes, which are then used in conjunction with dienophile monomers to produce a branching point, as per Scheme 6. The dienophile monomer can be a mixture of anionic monomers and hydrophobic uncharged monomers. The multifunctional aromatic systems can be small, such as 1,3,5- triethynylbenzene, or larger, having more than one aromatic group. The multifunctional aromatic systems can include heteroaromatic rings, such as pyridine (shown below) or

x x = 0, 1, 2, or 3 In some embodiments, the multifunctional aromatic systems can include a central heteroatom, such as nitrogen or carbon, as shown below. 2296-P5WO 49 In some embodiments, the terminal acetylene groups are replaced by H. Further examples of multifunctional aromatic systems are shown below, based on hexa- or pentaphenylbenzene compounds, which give rise to up to penta- or hexa- functional linkers. Y Y Y Y Y

Y^{= H or acetylene} In some embodiments, the branched polymers of the present disclosure can be made using monomers having 3 or more ketone moieties, such as a compound of Formula (XI), shown below: 2296-P5WO 50 R_1B

w^{herein R} _1A ^{and R} _1B ^{, at each occurrence, are as defined above, and provided that} ^{at least one (e.g., at least 2) of R} _1A ^{and R} _1B ^{is independently aryl or heteroaryl substituted} _{with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}- ^{X+, where X+ are as defined above. In some embodiments, R} _1A ^{and R} _1B ^{are absent, such} that the monomer of Formula (XI) is hydrophobic and uncharged, as in the monomeric unit (y) having Formula (II). The multi-functional linker or monomers described herein can be used as one of the starting materials in a reaction mixture to provide a branched polymer. The multifunctional linker can be present in an amount of 0.001 to 20 mole percent relative to the compound of Formula (I) or Formula (II). In some Formula (V):

P₂ (V), 2296-P5WO 51 ^{wherein P} ₁ ^{and P} ₂ ^{are independently selected from a repeat unit (x) of Formula (I)} and a repeat unit (y) of Formula (II), and wherein the repeat unit (x) of Formula (I) and repeat unit (y) of Formula (II) are as described herein. I^{n some embodiments of Formula (V), the ratio of z/(x+P} ₁ ^+P ₂ ^{) is less than 0.2.} In some embodiments, the copolymer is a random block copolymer, comprising: a first block selected from a first re+peating unit (x): SO X X+ 3 SO₃

, , and any combination thereof; and a second block selected from the second repeating unit (y): 2296-P5WO 52 , , and any combination thereof, wherein: n is an integer of from 3 to 100, m is an integer of from 3 to 100; and wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. The present disclosure features a method of making a random copolymer, comprising forming a mixture of a first repeating unit (x) of Formula (VI): 2296-P5WO 53 R_1E A wherein:

R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from _{C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, and provided that} ^{at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-_X ⁺ _; A₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, or heteroaralkylene is unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} 2296-P5WO 54 ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} X⁺ _{is a cation; and} A is a reactive first terminal group, and a second repeating unit (y) of Formula (VII): B

wherein R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from ^C _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, and cyano;} ^B ₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, B₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; K₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} 2296-P5WO 55 ^K ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; K₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; and B is a second reactive terminal group configured to react with A, and reacting A and B to provide a random copolymer of Formula (III): y

(III), wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. The present disclosure features a method of making a random copolymer, comprising forming a mixture of a first repeating unit (x) of Formula (VI):

(VI) wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from _{C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, and provided that} ^{at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} 2296-P5WO 56 _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-_X ⁺ _; A₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, or heteroaralkylene is unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} X⁺ _{is a cation; and} A is a reactive first terminal group, and a second repeating unit (y) of Formula (VII): B

(VII) 2296-P5WO 57 wherein R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from ^C _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, and cyano;} ^B ₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, B₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; K₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; K₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; and B is a second reactive terminal group configured to react with A, and reacting A and B to provide a random copolymer of Formula (III):

1_B y R_3E 2296-P5WO 58 (III), wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. provided that the repeating unit (x) of Formula (I) is not: SO X+

. The present disclosure features, inter alia, a compound of Formula (VII)

wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} _{alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided that at least} ^{two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl substituted} _{with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}- _X ⁺ _; A₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and 2296-P5WO 59 ^A ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. The present disclosure features, inter alia, a compound of Formula (VII) R R _1E

wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} _{alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided that at least} ^{two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl substituted} _{with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}- _X ⁺ _; A₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and A₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, the compound of Formula (VII) is not 2296-P5WO 60 SO X+ 3

. The compounds of Formula (VII) described herein include a compound of Formula (VII-A)

wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from _{C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided that at} ^{least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{; and} R_2A ^{, R} _2B ^{, R} _2C ^{, and R} _2D ^{are independently selected from H, halo, nitro, cyano, aryl,} and heteroaryl. The compounds of Formula (VII) described herein include a compound of Formula (VII-A) 2296-P5WO 61 R R _1E _1D wherein:

R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from _{C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, provided that at} ^{least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{; and} R_2A ^{, R} _2B ^{, R} _2C ^{, and R} _2D ^{are independently selected from H, halo, nitro, cyano, aryl,} and heteroaryl, provided that the of Formula is not +

. The present disclosure further describes a method of making any of the polymers disclosed herein, including forming a mixture of a compound of Formula (VII) and at least one compound of Formula (VIII), D₁ L₁ L₂ L₃ D₂ (VIII) wherein 2296-P5WO 62 ^L ₁ ^{is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^D ₁ ^{and D} ₂ ^{are independently H, R} _1G ^{, R} _1H ^{, R} _3G ^{, R} _3H ^{, or a protecting group (e.g.,} silyl protecting group, substituted silyl protecting group, trialkylsilyl protecting group, silyl ether protecting group, trialkyl silyl ether protecting group, trimethyl silyl ether), wherein ^R _1G ^{and R} _1H ^{are as defined herein, and wherein R} _3G ^{and R} _3H ^{are as defined herein; and} reacting a compound of Formula (VII) or (VII-A), and at least one compound of Formula (VIII), by Diels Alder reaction provide the polymer described herein. In some embodiments, the method of making any of the polymers described above includes reacting a compound of Formula (VII) and a compound of Formula (VIII) by Diels Alder, comprising heating the mixture to a temperature of from 150 °C to 300 °C (e.g., 180 °C to 230 °C) for a duration of 5 minutes to 30 days (e.g., 60 minutes to 7 days). The method can further include deprotecting the compound of Formula (VIII) before or during ^{the Diels Alder reaction, when at least one of D} ₁ ^{and D} ₂ ^{is a protecting group.} In certain embodiments, the mixture in the methods described above further comprise a compound of Formula

R _3C _3B

(IX) wherein 2296-P5WO 63 ^R _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from ^C _1-12 ^{alkyl and halo;} ^B ₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and B₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, the mixture in the methods described above further includes a compound of Formula (IX-A):

wherein: R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from ^C _1-12 ^{alkyl and halo; and} ^R _4A ^{, R} _4B ^{, R} _4C ^{, and R} _4D ^{are independently selected from H, halo, nitro, cyano, aryl,} or heteroaryl. The present disclosure further describes, inter alia, a method of making a random block copolymer, including unit (x) of Formula (VI) A

(VI) 2296-P5WO 64 ^{wherein R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, R} _1F ^{, R} _1G ^{, R} _1H ^{, A} ₁ ^{, A} ₂ ^{, L} ₁ ^{, L} ₂ ^{, and L} ₃ ^{are as} defined herein,

n is an integer of from 3 to 100, and A is a reactive first terminal group; and a second repeating unit (y) of Formula (VII)

wherein R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, R} _3F ^{, R} _3G ^{, R} _3H ^{, B} ₁ ^{, B} ₂ ^{, K} ₁ ^{, K} ₂ ^{, and K} ₃ ^{are as defined} herein, m is an integer of from 3 to 100, and B is a second reactive terminal group configured to react with A, and reacting A (e.g., an alkyne (reactive with a tetracyclone) or a tetracyclone (reactive with an alkyne)) and B (e.g., a tetracyclone or an alkyne) to provide a random block A B

(X), wherein the mole percent of the first repeating unit (x) of the first block is about 75% to about 99%, and the mole percent of the second repeating unit (y) of the second block is about 25% to about 1%. Membranes As disclosed herein, ionomeric copolymer membranes, comprising ionomeric copolymers having both hydrophilic and hydrophobic monomeric repeat units, exhibit 2296-P5WO 65 decreased water uptake and swelling, yet exhibit minimal impact on proton conductivity and electrochemical performance, relative to ionomeric polymer membranes comprising solely hydrophilic ionomeric monomers, or ionomeric copolymers having a composition outside the range 75% - 99% monomer (x) of Formula (I) and 25% - 1% monomer (y) of Formula (II). The composition 75% - 99% monomer (x) of Formula (I) and 25% - 1% monomer (y) of Formula (II) comprises property relationships which contrast with the expected, and previously observed, proportional decreases in proton conductivity and electrochemical performance for molecular compositions which exhibit decreased water uptake and swelling. The present disclosure features, inter alia, a membrane comprising any of the copolymers as disclosed herein. The present disclosure features, inter alia, an ionomer comprising any of the copolymers as disclosed herein. In some embodiments, the copolymers disclosed herein are incorporated into a membrane to form an ionomeric copolymer membrane. In some embodiments, the ionomeric copolymer membrane comprises a standalone ionomeric copolymer formed into a membrane through solvent casting or another process. In some embodiments, the ionomeric copolymer membrane comprises multiple ionomeric copolymers (e.g., ionomeric copolymers of different compositions) formed into a membrane through solvent casting or another process. In some embodiments, the ionomeric copolymer membrane is an ionomeric binder. In some embodiments, the ionomeric copolymer membrane is a substrate. In some embodiments, the ionomeric copolymer membrane is a mechanical reinforcement. In some embodiments, the ionomeric copolymer membrane is a combination of the foregoing. In some embodiments, the ionomeric binder is coupled to a substrate, directly or indirectly, through physical contact and/or interconnection, covalent bonding, ionic bonding, hydrogen-bonding, Van der Waals forces, and/or metallic bonding. In some embodiments, the ionomeric binder is coupled to a mechanical reinforcement, directly or indirectly, through physical contact and/or interconnection, covalent bonding, ionic bonding, hydrogen-bonding, Van der Waals forces, and/or metallic bonding. The mechanical reinforcement or the substrate can comprise a porous polymeric material. The porous polymeric material can be any polymeric material comprising pores. The porous polymeric material can be, for example, a linear sulfonated phenylated 2296-P5WO 66 poly(phenylene) ionomer, such as a linear sulfonated phenylated poly(phenylene) biphenyl (sPPB-H⁺) ionomer, an ionomeric copolymer as disclosed herein, expanded polyethylene (ePE), and/or expanded polytetrafluoroethylene (ePTFE). The ionomeric binder can comprise an ionomeric copolymer as described herein, such as the ionomeric copolymer of Formula (III) or Formula (IV). The ionomeric copolymer of the ionomeric binder can comprise an amount of from about 0.5 wt% to about 99 wt%, about 0.5 wt% to about 50 wt%, about 0.5 wt% to about 25 wt%, or about 0.5 wt% to about 15 wt% of solids. In some embodiments, the ionomeric copolymer membrane further comprises a catalyst layer. The catalyst layer can be applied to the ionomeric copolymer membrane to form a catalyst-coated ionomeric copolymer membrane, wherein the catalyst layer is in contact with the ionomeric copolymer membrane, the ionomeric binder of the ionomeric copolymer membrane, or the mechanical reinforcement of the ionomeric copolymer membrane. In some embodiments, the catalyst layer comprises a combination of a catalyst (e.g. Pt/C, PtCo/C, M-N-C catalyst) and ionomeric copolymer. In some embodiments, the catalyst layer further comprises additives. In some embodiments, the catalyst layer is formed from a catalyst ink. In some embodiments, the catalyst layer is formed from a catalyst ink formulation comprising an ionomeric copolymer as disclosed herein, and a catalyst (e.g. Pt/C, PtCo/C, M-N-C catalyst). In some embodiments, the catalyst of the catalyst ink formulation comprises platinum on carbon supports (i.e., Pt/C) of various Pt particulate sizes in combination with carbon materials of various surface areas and sizes. In some embodiments, the catalyst of the catalyst ink formulation comprises Pt alloys on carbon supports (e.g., PtCo/C) of various precious metal alloy particulate sizes and alloy ratios in combination with carbon materials of various surface areas and sizes. In some embodiments, the catalyst of the catalyst ink formulation comprises M-N-C catalysts, incorporating non-precious-metal ions (e.g., wherein M is iron or cobalt) within a nitrogen-doped carbon support. As used herein, the wt% of Pt/C catalyst means the total amount of the Pt/C solids used, including both the Pt and carbon amount. For example, the wt% of Pt/C remains the 2296-P5WO 67 same for a total mass used whether the Pt/C is 40 wt% Pt and 60 wt% carbon, or a different relative composition. In some embodiments, the amount of catalyst used is between about 0.1 wt% and about 2.0 wt% based on solids content. In some embodiments, the amount of catalyst used is between about 0.1% w/v and about 25% w/v catalyst (e.g., Pt/C, PtCo/C, and M-N-C catalyst) relative to the catalyst ink solvent volume. In some embodiments, the catalyst ink composition comprises between about 1 wt% and about 30 wt% ionomeric copolymer, and between about 70 wt% and about 99 wt% of supported catalyst, of total solids content. In some embodiments, the catalyst ink composition comprises between about 10 wt% and about 30 wt% ionomeric copolymer, and between about 70 wt% and about 90 wt% of supported catalyst, of total solids content. In some embodiments, the catalyst layer comprises between about 1 wt% and about 30 wt% ionomeric polymer, and between about 70 wt% and about 99 wt% of supported catalyst or solids content. In some embodiments, the ionomeric copolymer as described herein is incorporated into a catalyst layer of a fuel cell, an electrolyzer, or another electrochemical device. A fuel cell, an electrolyzer, or another electrochemical device can comprise a catalyst layer comprising an ionomeric copolymer as described herein. For example, in some embodiments, the copolymer is incorporated into a catalyst layer of a fuel cell, an electrolyzer, or another electrochemical device in an amount of from about 5 wt% to about 45 wt% solids, from about 10 wt% to about 45 wt %, from about 15 wt% to about 45 wt %, from about 30 wt% to about 45 wt %, from about 5 wt% to about 30 wt %, from about 15 wt% to about 45 wt %, from about 30 wt% to about 45 wt %, from about 10 wt% to about 30 wt %, from about 10 wt% to about 20 wt %, or from about 15 wt% to about 30 wt % in the catalyst layer. The ionomeric polymer membrane can have a top surface and a bottom surface, such as would exist in a formation such as a sheet, including a sheet which is rolled, folded, or distorted in another manner. In some embodiments, the catalyst layer is in contact with only the top surface of the ionomeric polymer membrane, only the bottom surface of the ionomeric polymer membrane, or both the top and bottom surface of the ionomeric polymer membrane. 2296-P5WO 68 When the catalyst layer is in contact with only the top surface or only the bottom surface of the ionomeric polymer membrane, a bi-layer is formed. The bi-layer can be used as a two-layered membrane electrode assembly. When the catalyst layer is in contact with both the top surface and the bottom surface of the ionomeric polymer membrane, a tri-layer is formed. The tri-layer can be used as a three-layered membrane electrode assembly. A bi-layered or tri-layered catalyst-coated ionomeric copolymer membrane can be in a form which is planar, such as a sheet. The sheet can be planar, rolled, folded, or distorted in another manner. For example, the catalyst-coated ionomeric copolymer membrane can be a sheet which is rolled up, to form a roll which can have dimensions such as 30 cm wide by a length such as 1 to 1000 meters, or a length such as 10 to 100 meters. In an embodiment, the catalyst layer of the catalyst-coated ionomeric copolymer membrane acts as an anode or a cathode. When only one surface of the ionomeric copolymer membrane is in contact with the catalyst layer, the catalyst layer is either an anode or a cathode. When both surfaces of the ionomeric polymer membrane are in contact with a catalyst layer, one catalyst layer is an anode and the other catalyst layer is a cathode. Generally, the anode is the electrode wherein oxidation occurs during an electrochemical reaction. The cathode is the electrode wherein reduction occurs during an electrochemical reaction. Whether a catalyst layer is an anode or a cathode can be determined by the orientation of the catalyst layer in a product such as a fuel cell. Whether a catalyst layer is an anode or a cathode can be determined by the combination of the orientation of the catalyst layer in a fuel cell and the amount of catalyst present. In a fuel cell, the anode is ^{the electrode where the fuel, such as hydrogen (H} ₂ ^{), is oxidized, releasing electrons and} _{protons (H} ⁺ _{). The electrons are then drawn through an external circuit to perform useful} _{work, while the protons (H} ⁺ _{) migrate through an electrolyte to the cathode. In a fuel cell,} the cathode is the electrode where oxygen (O₂) is reduced, combining with protons (H⁺) ^{from the electrolyte to form water (H} ₂ ^O). ^{In an electrolyzer, an anode is the electrode wherein water (H} ₂ ^{O) is oxidized} through an electrochemical reaction to produce oxygen (O₂), protons (H⁺), and electrons _(e-_). 2296-P5WO 69 _{In an electrolyzer, the cathode is the electrode wherein protons (H} ⁺ _{) are reduced} ^{via electrochemical reaction to produce hydrogen gas (H} ₂ ^). In some embodiments, the ionomeric copolymer membrane has a proton _{conductivity (e.g., ex situ conductivity, in-plane) of from about 0.001 mS cm} ^-1 _{to about} _{1000 mS cm} ^-1 _{, from about 0.001 mS cm} ^-1 _{to about 750 mS cm} ^-1 _{, from about 0.001 mS} _cm ^-1 _{to about 450 mS cm} ^-1 _{, from about 1 mS cm} ^-1 _{to about 1000 mS cm} ^-1 _{, of more than} _{about 0.001 mS cm} ^-1 _{, of more than about 1 mS cm} ^-1 _{, or of less than about 1000 mS cm} ^{- 1} _, at a relative humidity of from 30 % to 100 % when measured using AC impedance spectroscopy (electrochemical impedance spectroscopy) at a temperature of between about 20 °C to about 90 °C, or between about 50 °C to about 90 °C. The ionic polymer membrane can have a proton conductivity (e.g., ex situ conductivity, in-plane) of from about 1 mS _cm ^-1 _{to about 1000 mS cm} ^-1 _{, or about 50 mS cm} ^{- 1} _{to about 450 mS cm} ^-1 _{at about 80 °C} in water when measured using AC impedance spectroscopy (electrochemical impedance spectroscopy). In some embodiments, the ionomeric copolymer membranes as described herein have an ion exchange capacity (IEC) of from about 2.4 to about 3.5 meq g^-1. In some embodiments, the ionomeric copolymer membranes as described herein have an ion exchange capacity (IEC) of from about 2.4 to about 2.9 meq g^-1, when evaluated by acid- base titration. For example, cation exchange of the acidic, or protonated, form (e.g., -SO₃- _H ⁺ _{) of the copolymer to the conjugate base sodium counterpart (e.g., -SO3}-_Na ⁺ _{) is} evaluated, by immersing samples in pH 7, 1 M NaCl solution for 48 h; then titrating the resulting acidic solution to pH 7 using a standardized titrant (e.g., 0.01 M NaOH solution). IEC can be calculated by using volume and molarity of titrant used, and dry mass of the sample being titrated. A person of ordinary skill in the art would understand that titration can also be performed with other bases (e.g., KOH solution), and the counterion cations can be exchanged, for example by exposure of a sulfonate sodium salt with, for example, _{KCl to result in complete or partial potassium salt (e.g., -SO3}-_K ⁺ _{) formation.} In some embodiments, the ionomeric copolymer membranes described herein exhibit a mass loss of less than about 20% or less than about 10% when exposed to Fenton's reagent at a temperature of 80 °C, at 1 atm, and for a duration of from greater than 0, to 180 minutes, or a duration of from greater than 0, to 90 minutes, or a duration of from greater than 0, to 60 minutes. 2296-P5WO 70 In some embodiments, the ionomeric copolymer membranes described herein exhibit a water uptake of 60 – 120 wt% at room temperature. In some embodiments, the copolymer of the present disclosure is incorporated into a cation exchange resin. In some embodiments, the copolymers disclosed herein, or the ionic copolymer membranes comprising the copolymers, are used in electrochemical devices, wherein the electrochemical device is a fuel cell, electrolyzer, hydrogen pump, thermoelectrochemical hydrogen pump, electrochemical hydrogen compressor, redox flow battery, or other electrochemical device. EXAMPLES Example 1 Copolymer Membrane Properties Four different ionomeric polymers of different acid functionalization were prepared via Diels-Alder polymerization – a 100% functionalized sulfonated polyphenylene ("100%-sPP"), a copolymer comprising 90% functionalized sulfonated polyphenylene and 10% non-sulfonated polyphenylene ("90%-sPP"), a copolymer comprising 80% functionalized sulfonated polyphenylene with 20% non-sulfonated polyphenylene ("80%- sPP"), and a copolymer comprising 70% functionalized sulfonated polyphenylene and 30% non-sulfonated polyphenylene ("70%-sPP"). Each ionomeric polymer was formed into membranes by a solvent casting process, and each membrane was evaluated for its ion- exchange capacity (IEC), mechanical properties, water sorption and dimensional stability, and proton conductivity. Unreinforced ex-situ membrane properties were measured at room temperature (22 ± 1 °C) and in hot state (80 °C) under dry (dried at 80 °C for at least 2 h), ambient (equilibrated under ambient laboratory conditions for at least 2 h), and/or wet (immersed in DI water for at least 30 min) conditions, as indicated. Water uptake samples were cut to specific dimensions (MD 5 cm x TD 4 cm), using a die cutter. The testing procedure followed ASTM standard D570. Water uptake was represented by percentage increase in weight during immersion, calculated to the nearest 0.01%, per Equation 1, where W_w is the weight of hydrated membrane and Wd is the weight of dry membrane. 2296-P5WO 71 Dimensional change with respect to the dry state is given by Equation 2, where Sx,y,z is the dimensional change in the machine direction, transverse direction, and membrane thickness. Dw is the specific dimension after immersion (typically in cm for the MD and TD, and in µm for the thickness), and D_d is the specific dimension in the dry state.

Masses were measured using an analytical balance reading to at least 0.1 mg. Thicknesses (defined as the z-dimension) were measured using a precision micrometer with a resolution of ± 1 µm, while the width and length (x and y dimensions) were measured using a ruler with 0.5 mm precision, or alternatively using a digital flatbed scanner and image analysis software (ImageJ or equivalent). The ionic resistance of membranes in the in-plane direction was measured with a two-point probe by applying an AC potential sweep over a range of 10⁷-10⁴ Hz using an impedance/gain-phase analyzer (Solartron SI 1260 or equivalent) on fully hydrated membranes immersed in liquid water, or at a specified temperature and relative humidity as controlled using an appropriate apparatus (typically an environmental chamber). The analyzer records electrochemical impedance, which can be inputted into a simplified Randles equivalent circuit. The ionic conductivity is calculated using Equation 3, where σ is the ionic conductivity (in Ω^-1∙cm^-1), l is the distance between the probes (in cm), A is the cross-sectional area of the membrane (in cm²), and R is the membrane resistance as determined by a fitting to a standard Randle's circuit model.

The ionic resistance of membranes in the through-plane direction was measured with a two-probe configuration utilizing a frequency range of 10 MHz to 100 Hz with an amplitude of 100 mV. The electrode area was 5x5 mm. Membrane resistance was obtained via fitting electrochemical impedance into a suitable simplified equivalent circuit (FIG.1). 2296-P5WO 72 Conductivity was calculated using Equation (3), where σ is the calculated conductivity of the membrane, l is the thickness of the test membranes, R is the resistance of the membrane measured, A is the active area. Mechanical properties were measured via tensile stress-strain pull tests utilizing samples of material which were cut by a roller die. Tensile stress is defined as the ratio between the load applied (extension) to a given cross-sectional area. The equation for tensile stress (σ, Equation 4) is the load applied (in Newtons) divided by the original cross- sectional area (A) of the sample. Tensile strain (represented by ^ in Equation 5) is the change in length over the elongation divided by the original length and it is typically presented as percentage of elongation. Mechanical properties of materials are characterized by plotting a curve of tensile stress versus strain. The slope of elastic region is the elastic (or Young's) modulus, and is calculated per equation 6.

Ion exchange capacities were measured by titration. Ionomeric polymer membrane samples (3 x 3 cm) in native acidic form were soaked in a solution of 1 M NaCl for 24 h. The resulting acidic solution was titrated with a solution of 0.01 M NaOH using phenolphthalein (1 wt% in ethanol) indicator. A minimum of 3 replicates were performed to obtain standard deviations. The IEC was calculated following Equation 7 below where VNaOH is equal to the volume at the equivalent point, MNaOH is the concentration of the NaOH solution, and Wdry is the mass of the dry membrane. ^^^^

^^^^ ^^^^ ^^^^ ^^^^ ^^^^ A summary of the measured properties of unreinforced membranes formed from the four ionomeric polymers of different acid functionalization, 100%-sPP, 90%-sPP, 80%- sPP, and 70%-sPP, is provided below in Table 1. 2296-P5WO 73 Table 1. Summary of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP unreinforced membrane properties. Membranes comprising copolymers of sulfonated polyphenylene with non- sulfonated polyphenylene (e.g., 90%-sPP, 80%-sPP, and 70%-sPP) exhibited dramatically reduced hydrophilicity, which yielded improved dimensional stability and reduced water uptake relative to membranes comprising a sulfonated polymer without presence of any hydrophobic monomer (e.g., 100%-sPP). However, reductions to electrochemical properties, namely ex-situ proton conductivity occurred. For example, 80%-sPP membranes exhibited a 28.3% reduction in proton conductivity, alongside a 52.0% 2296-P5WO 74 reduction in volumetric swelling and 28.1% reduction in water uptake, at room temperature, compared to that of 100%-sPP. In contrast, the 90%-sPP membranes exhibited on average only 11.0% reduced proton conductivity compared to that of 100%-sPP, with a concurrent 43.5 wt% and 43.0 vol% reduced water uptake and volumetric swelling, respectively. This indicates a more advantageous and significantly disproportionate trade-off in reduced proton conductivity relative to reduced water sorption parameters, and deviates from the expected linear relationship. These findings are further corroborated by cyclic swelling/deswelling tests, wherein membranes of each polymer were repeatedly soaked in water at 80 °C for 4 hours to swell, measured for changes to their dimensions (thickness and membrane area) and water uptake, then dried in an oven at 80 °C for 4 hours to de-swell (FIG.2). Data are provided in FIG. 3. Compared to any copolymer of sulfonated polyphenylene and non-sulfonated polyphenylene disclosed herein, membranes of the sulfonated polyphenylene (100%-sPP) exhibited large changes in thickness (S_z up to 165%), length (S_x up to 64% length), width (Sy up to 57% width), and water uptake (up to 475 wt%) with each swell/deswell cycle, indicating measurable dimensional instability. In contrast, 90%-sPP membranes exhibited a nearly 50% reduction to thickness swelling (i.e., Sz up to 92%), ~40% reduction to length and width swelling (i.e., S_x and S_y up to 40 and 37%, respectively), and 47% reduced water uptake (i.e., up to 250 wt%). 80%-sPP and 70%-sPP membranes demonstrated further stepwise decreases in membrane water sorption (175 and 120 wt%, respectively) and dimensional swelling (S_z up to 83%, S_x up to 28%, S_y up to 29.5%, and S_z up to 79%, S_x up to 14%, S_y up to 16.5%, respectively) but the decreases were of lesser magnitude than when comparing the step from 100%-sPP to 90%-sPP. Example 2 Reinforced Membrane Properties Reinforced (composite) ex-situ membrane properties were evaluated using methods described above. As observed in the case of unreinforced membranes, the overall water uptake and swelling behavior (FIGs 4 and 5) of reinforced membranes comprising 90% functionalized copolymers of sulfonated polyphenylene and non-sulfonated polyphenylene (90%-sPP) were significantly reduced compared with those comprising 100% 2296-P5WO 75 functionalized sulfonated polyphenylenes (100%-sPP), although the swelling behavior was predominantly observed in the thickness (z) direction due to the reinforcing and mitigating effects of the mechanical reinforcement utilized in both. For instance, at rt (22 ± 2 °C), reinforced membranes of 90%-sPP exhibited 109.7 ± 18.6 wt% water uptake and 127.6 ± 11.2% thickness swelling, whereas reinforced membranes of 100%-sPP exhibited 139.7 ± 6.5 wt% water uptake and 149.9 ± 4.7% thickness swelling. Similarly, at 80 °C, reinforced membranes of 90%-sPP exhibited 156.9 ± 18.9 wt% water uptake and 170.8 ± 11.6% thickness swelling, whereas reinforced membranes of 100%-sPP exhibited 217.6 ± 7.1 wt% water uptake and 225.1 ± 3.9% thickness swelling. Hence, appreciable reductions at both rt and 80 °C, in both water uptake (21.5 and 27.9%, respectively) and thickness swelling (14.8 and 24.1%, respectively) were observed in 90%-sPP vs. that of 100%-sPP reinforced membranes. However, despite the reduced acid functionalization in 90%-sPP, and hence an expected reduction in electrochemical performance compared with 100%-sPP, no statistically significant differences in both in-plane conductivity (90%-sPP = 122 ± 7 mS/cm, 100%-sPP = 113 ± 7 mS/cm) as well as through-plane conductivity (90%-sPP = 114 ± 9 mS/cm, 100%-sPP = 129 ± 11 mS/cm) occurred for the composite membranes evaluated (FIG.6). The water uptake and swelling data are further corroborated by cyclic swelling/deswelling tests, as was observed in unreinforced membrane analogues described in Example 1. Mechanically reinforced membranes of 100%-sPP and 90%-sPP were subject to the swell/deswell test outlined in FIG.2, and data are shown in FIG.7. Significant differences were observed between the 100%-sPP ionomeric polymer and 90%-sPP ionomeric copolymer, wherein the 90%-sPP copolymer exhibited markedly reduced thickness swelling and improved dimensional stability over the course of the experiment. For example, while 100%-sPP exhibited a maximum thickness swelling (Sz) of 324% over the course of the experiment, 90%-sPP exhibited a maximum thickness swelling (S_z) of 248%. Over the course of the experiment, the difference in thickness swelling between 100%-sPP and 90%-sPP was 23.6 ± 7.9%. That is to say, at any given point during the experiments, the thickness swelling of 100%-sPP was approx.1.25x that of 90%-sPP. This further highlighted the unexpected, emergent properties of the reduced functionalization of the 90% sulfonated polyphenylene and 10% non-sulfonated polyphenylene copolymer (90%-sPP). 2296-P5WO 76 Example 3 Non-reinforced in-situ Membrane Properties Non-reinforced in-situ membrane properties were evaluated by conducting fuel cell tests following a standardized protocol, as described below. Catalyst inks were prepared using Pt/C catalyst powder (TKK TEC-10e40e, 36.9 wt% Pt on graphitized carbon), 2:1 IPA:H₂O solvent, and ionomer solution (Nafion D520). The final catalyst ink mixtures contained 1 wt% solids (0.70 wt% Pt/C catalyst powder and 0.30 wt% ionomer) in 2:1 IPA:H2O. Ultrasonic spray coating (Sono-Tek ExactaCoat SC) was then used to prepare catalyst coated membranes of 5 cm² electrode area atop specific membranes, with target Pt loadings of 0.4 mg cm^-2 at each of the cathode and anode. Catalyst coated membranes were integrated into fuel cell hardware using commercial gas diffusion layers with microporous layers (Freudenberg H14C15) and polyimide gasketing (100 μm total). The testing was performed using TP5eV2 hardware produced by Tandem Technologies, utilizing a bladder pressure system optimized for 160 psi compression, which was determined by monitoring area specific resistance as a function of compression until no further reductions were measured. A Teledyne Medusa RD, Model 890CL fuel cell test station (Scribner Assoc. Inc.) was used for in-situ fuel cell characterization. After assembly of the fuel cell, the humidifiers and cell temperature were set to 80 ̊C, and a nitrogen purge was conducted for 5 minutes. The gas feeds were then switched to H2/Air at 0.25/0.5 SLPM flows, and both gases were pressurized to 150 kPag. Cell open circuit voltage (OCV) was monitored, and once stabilized, current was slowly ramped by 5 mA/s increments until a potential of 0.65 V was reached. Thereafter, 30 cycles of 0.6V, 0.3V, and 0.05A (1 min per step for a total of 1.5 hrs) were performed for cell break in. Polarization data were measured by holding cells at 80 °C under pure H2/Air (0.25/0.5 slpm flows) at 150 kPa_g backpressure, and relative humidities (RH) of 100/100 %RH, 100/30 %RH, or 30/30 %RH (anode|cathode), as indicated, and ramping cells from 0 A to 15 A, at a rate of 3 min/pt and 1 pt/step. In each case, the average current over the three min was recorded. Electrochemical measurements were performed utilizing a VersaStat Potentiostat, with the cell and humidifiers held at 80 ̊C (100/100 %RH), and each of the input gases H2/N2 (anode|cathode) run at 0.5 SLPM, and 150 kPag. Linear sweep voltammetry was 2296-P5WO 77 measured once the cell's potential was stable below 0.150 V. A voltage sweep from 0.1 to 0.6 V at a scan rate of 0.005 V/s was performed to ensure there was no short in the cell. Chronoamperometry measurements were used to measure hydrogen crossover current of the cell, by ramping voltage 0.1 to 0.6 V with 60 second holds at each step, except for an extended 120 second hold at 0.5 V. The average current recorded during the last 60 second phase of the 0.5 V hold was used as the final hydrogen crossover current, from which current density was derived by dividing by the active area of the cell, resulting in a unit of mA/cm². The performance of the specific membrane electrode assemblies (MEAs) evaluated, comprising gas diffusion layers as described, microporous layers, and electrode configurations, but having different membranes, are reported as maximum power density (mW/cm²) and area-specific resistance (mΩ/cm²). Membranes of 100%-sPP (44.0 μm), 90%-sPP (45.5 μm), 80%-sPP (39.5 μm), and 70%-sPP (45.0 μm) were compared to a Nafion^® XL baseline reference. Performance (I-V) curves are shown in FIG. 8. Two different gas diffusion layers (GDL), H15C14 (11% compression) and AvCarb 3250 (29% compression), were used for the polymer series and Nafion^® XL, respectively. The hydrocarbon ionomeric copolymer membranes exhibited slightly greater losses in the activation region of respective polarization curves, but comparable or lower losses in the ohmic and mass transport regions, when compared to Nafion^® XL (See Table 2). The area resistances of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP, and Nafion^® XL were 79.66, 52.26, 63.82, 52.97 and 51.64 mOhm/cm² (offset R not taken off), respectively, determined by IR-drop method in the ohmic region at 1.6 A/cm². The 80%-sPP membranes exhibited higher area resistance, but also demonstrated comparable performance. Gas crossover currents measured for 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP, and Nafion^® XL were 0.76, 1.07, 1.06, 1.49 and 4.27 mA/cm², respectively. Consequently, the hydrocarbon membranes reliably demonstrated ~3-4x reduced gas crossover versus the PFSA baseline. The maximum power densities of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP, and Nafion^® XL were 1.33, 1.68, 1.64, 1.61 and 1.64 W/cm², respectively, under full humidification. These measurements were performed with cell configurations optimized for PFSAs, incorporating fully PFSA-compatible electrodes and highly PFSA- optimized catalyst and ionomer loadings. See Table 2 for recited data. Table 2. Summary of MEA Constituents and Fuel Cell Test Conditions (H2/O2). 2296-P5WO 78 When evaluated under H₂/Air with moderate backpressure (150 KPa_g), the 100%- MEA 100%-sPP 90%-sPP 80%-sPP 70%-sPP Nafion XL Cathode D520 D520 D520 D520 D520 Ionomer (wt%) 30 30 30 30 30 Loading Pt/C (mg/cm²) 0.4 0.4 0.4 0.4 0.4 Membrane 100%-sPP 90%-sPP 80%-sPP 70%-sPP Nafion XL Thickness(um) 44.0 45.5 39.5 45 27.5 Anode D520 D520 D520 D520 D520 Ionomer (wt%) 30 30 30 30 30 Loading Pt/C (mg/cm²) 0.4 0.4 0.4 0.4 0.4 Flow rate (L/min) 0.25/0.5 0.25/0.5 0.25/0.5 0.25/0.5 0.25/0.5 Current Interrupt resistance 79.66 52.26 63.82 52.97 51.64 at 1.6 A/cm² (mOhm/cm²) In-situ conductivity by IR- 55.0 87.1 61.9 85 53.3 drop (non-offset) (mS/cm) In-situ conductivity by EIS 113.40 76.98 72.35 5.67 111.07 (mS/cm) Gas crossover initial (mA/cm²) 1.09 2.12 2.00 2.18 5.50 Gas crossover post (mA/cm²) 0.76 1.07 1.06 1.49 4.27 Powder density (mW/cm²) 1332 1680 1640 1610 1640 sPP, 90%-sPP, 80%-sPP, and 70%-sPP membranes showed greater losses in the activation and ohmic regions of the polarization curve, per FIG. 9. However, Nafion^® XL showed greater losses in the mass transport polarization region when the current density surpassed 2 A/cm² (See Table 3). Generally, 90%-sPP performed better than 100%-sPP, 80%-sPP and 70%-sPP in the mass transport region, possibly due to water transport and self- humidification of the membrane, and its higher proton conductivity. However, the IR 2296-P5WO 79 resistances for the equally thick membranes across the ohmic region were very similar, but increased in the mass transport region, suggesting that the current flow rate is good and can avoid producing excess water which may flood the electrodes. The area resistances of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP and Nafion^® XL were again similar: 71.31, 51.75, 63.82, 51.24 and 50.41 mOhm/cm² (offset R not taken off), respectively. The maximum power densities of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP and Nafion^® XL were 988, 1013, 968, 882 and 966 mW/cm², respectively. All above data are listed in Table 3. Table 3. Summary of MEA constituents and fuel cell test conditions (H2/Air, 150 KPa_g). MEA 100%-sPP 90%-sPP 80%-sPP 70%-sPP Nafion XL Cathode D520 D520 D520 D520 D520 Ionomer (wt%) 30 30 30 30 30 Loading Pt/C (mg/cm²)^b 0.4 0.4 0.4 0.4 0.4 Membrane 100%-sPP 90%-sPP 80%-sPP 70%-sPP Nafion XL Thickness(um) 44.0 45.5 39.5 45 27.5 Anode D520 D520 D520 D520 D520 Ionomer (wt%) 30 30 30 30 30 Loading Pt/C (mg/cm²)^b 0.4 0.4 0.4 0.4 0.1 Flow rate (L/min) 0.25/0.5 0.25/0.5 0.25/0.5 0.25/0.5 0.25/0.5 Current Interrupt resistance at 71.31 51.75 63.82 51.24 50.41 1.6 A/cm² (mOhm/cm²) In-situ conductivity by IR-drop 61.8 87.9 59.6 81 54.6 (non-offset) (mS/cm) Powder density (mW/cm²) 988 1013 968 882 966 When cell backpressure was increased from 150 KPag (21.75 psi) to 300 KPag (43.51 psi), increased water production in the cathode appeared to better humidify all ionomeric polymer membranes, and resulted in lower losses in the mass transport polarization region, which yielded the higher performance (see FIG. 10). Again, 100%- 2296-P5WO 80 sPP, 90%-sPP, 80%-sPP, and 70%-sPP showed greater losses in activation polarization, but lower losses in ohmic polarization compared to that of Nafion^® XL. The area resistances of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP and Nafion^® XL at 300 KPa_g (74.4, 50.4, 61.8, 50.8 and 49 mOhm/cm² (offset R not taken off), respectively) were slightly lower than under H2/Air at 150 KPag. The maximum power densities of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP were 1.05, 1.16, 1.07 and 1.10 W/cm², respectively, which represented increases of 6.16%, 13.46%, 9.71% and 13.1%, respectively, versus the same membranes evaluated at 150 KPag backpressure. In contrast, the Nafion^® XL showed a 1.65% decrease in performance, measuring 0.95 W/cm² under the same conditions. Generally, the performance of the ionomeric polymer membrane series under all conditions followed the order 90%-sPP > 100%-sPP = 80%-sPP > 70%-sPP. The higher performance of 90%-sPP, and subsequent equivalence between 100%-sPP and 80%-sPP, were unexpected and represent a meaningful differentiated material property in the 90%-sPP copolymer. Finally, the ionomeric copolymer membranes were evaluated at 80 °C, 30% RH under H2/Air, 150 KPag, as shown in FIG.11. The performance of all of the copolymers of ionomeric monomers and hydrophobic monomers decreased at reduced relative humidity, whereas IR resistances increased. All of the ionomeric copolymer membranes showed greater losses in the ohmic region of respective polarization curves, and universally measured lower than Nafion^® XL, due to high area resistance values. Membranes of 90%- sPP again demonstrated differentiated power density in the order of 90%-sPP > 80%-sPP > 70%-sPP. The area resistances of 90%-sPP > 80%-sPP > 70%-sPP and Nafion^® XL were 154, 243, 188 and 95 mOhm/cm² (offset R not taken off), respectively, with maximum power densities measuring 584, 444, 478, and 934 mW/cm², respectively. These values represent decreases of 53.8%, 74.2% and 59.5% in performance versus those obtained at 100% RH. It was not possible to generate data at 80 °C, 30% RH under H₂/Air, 150 KPa_g, for 100%-sPP unreinforced membranes due to consistent mechanical failures observed below 50% RH under the conditions (e.g., high stoichiometries) used in standard fuel cell testing. The data generated, in addition to the failures observed in the case of 100%-sPP, further highlight the meaningful differentiated material properties of the ionomeric copolymer membranes. 2296-P5WO 81 Example 4 Reinforced in-situ Membrane Properties Reinforced in-situ membrane properties were evaluated by conducting fuel cell tests following a standardized protocol, as described above in Example 3. The performance of the specific membrane electrode assemblies (MEAs) evaluated, comprising identical gas diffusion layers, microporous layers, and electrode configurations, but different membranes, are reported as maximum power density (mW/cm²) and area-specific resistance (mΩ/cm²). In all cases, there were no statistically significant differences in performance observed between MEAs containing reinforced membranes with 100% functionalized sulfonated polyphenylenes (100%-sPP, n=8) vs. 90% functionalized copolymers of sulfonated polyphenylene and non-sulfonated polyphenylene (90%-sPP, n=9), despite a 10% reduction in acid group functionalization (FIGs 12 and 13). Example 5 Ionomeric Copolymer Synthesis and Properties The sPP ionomeric copolymers were prepared on a 3 g scale. After preliminary evaluation of polymer solubility and membrane properties, each copolymer was scaled to 20 g (monomers). The up-scaled syntheses were projected to produce 12-14 g of each ionomeric copolymer. However, the yield of 70%-sPP was noticeably lower than expected due to challenges associated with its limited solubility in polar solvents (Table 1). The viscosity of the produced ionomeric copolymers decreased with increasing hydrophobic monomer content. The viscosity of the produced ionomeric copolymers also correlated to polymer molecular weight. This result indicated a reduction in molecular weight led to the reduced solubility of the polymer during its polymerization and ion exchange processes. 2296-P5WO 82 Table 4. Summary of ionomeric copolymer yield and viscosity properties. Copolymer Yield (%) Viscosity (cP) 100%-sPP 89 10.5 90%-sPP 98 11.4 80%-sPP 97 10.5 70%-sPP 63 7.2 Example 6 Ionomeric Monomer Unit Synthesis In some embodiments, a polyphenylene precursor compound of the present disclosure can be made according to Scheme 1. Scheme 1. General scheme for making a precursor compound to a polyphenylene ^{of the present disclosure ([HN(CH} ₂ ^CH ₃ ⁾ ₃ ^{]+ is shown as a non-limiting example of a cation)} ₂

where: (^{i) KOH, EtOH, reflux; (ii) Me} ₃ ^SiOSO ₂ ^{Cl, 1,2-dichloroethane; (iii) Et} ₃ ^{N, n-BuOH;} and Ar is arylene, heteroarylene, aralkylene, or heteroaralkylene, or two of these linking moieties linked to one another to form a linking moiety having two linked aromatic groups. Ar is arylene. The tetraketone of Scheme 1 can be made via the synthetic procedure below. Scheme 2. General synthetic scheme for a tetraketone. 2296-P5WO 83 O X X O where: (^{iv) Pd(PPh} ₃ ⁾ ₂ ^Cl ₂ ^{, CuI, HNEt} ₂ ^{; (v) I} ₂ ^{, DMSO, reflux; and Ar is as defined above} for Scheme 1. Examples of X-Ar-X compounds include, for example, Br Br I

As an example, when used as a starting material in Schemes 2 and 1, the resulting precursor

4_X ⁺ _{, when compound 2A is used as X-Ar-X.} As another example, when used as a starting material in Schemes 2 and 1, the resulting precursor compound can be 2296-P5WO 84 SO₃ - - w_{hen compound 6 is used as X-Ar-X.}

In some a present disclosure can be made via Scheme 3 (showing as an example, a naphthyl-linked polyphenylene), where a protecting group, such as TMS (tetramethylsilyl ether) is first removed from a dialkyne compound, then the resulting dialkyne is reacted via Diels-Alder reaction with a precursor compound to provide the polymer. Scheme 3. Synthesis of a naphthyl-linked polyphenylene. - - + -

₃O₃S In some embodiments, rather than first deprotecting a dialkyne compound, the deprotection occurred in situ, during polymerization (e.g., Scheme 4). 2296-P5WO 85 Scheme 4. In S s Oitu deprotection of a protected dialkyne compound. 3 - - O ^SO ₃ ^SO ₃ - + 3 -

some are following synthetic scheme. Scheme 5. Organometallic catalyst-mediated coupling to provide an exemplary polymer of the present disclosure. While one embodiment of a polymer is shown below, a person of ordinary skill in the art would understand that polymers with other claimed linkers can be readily obtained using analogous synthesis methods as that shown in the present scheme. 2296-P5WO 86

Some exemplary linkers useful for the organometallic catalyst-mediated coupling ,

. Example 7 2296-P5WO 87 Branched Polymer Synthesis As discussed above, in some embodiments, the polymers of the present disclosure are branched. Without wishing to be bound by theory, in some embodiments, branched polymers can have improved properties over their linear polymer analogues. The branched polymers can have a multivalent linker that is directly covalently bound to at least 3 repeating units (e.g., anionic, hydrophobic, or a combination thereof). The branched polymers can be synthesized through addition of multi-functional linkers (e.g., dienophiles) having 3 reactive functional groups or more, such as outlined for a tri-functional monomer in Scheme 6(b), below. Scheme 6(a) shows the synthesis for a linear sulfonated polymer. Schemes 6(a) and 6(b). Sulfonated, phenylated polyphenylenes using a tri- functional monomer to induce branching. 2296-P5WO 88 - (a) SO₃

A representative tri- ' 3

D₂ wherein L₃ ^{' at each occurrence, is an unsubstituted or substituted multivalent heteroatom} (e.g., N, P, B), multivalent aryl, multivalent heteroaryl, multivalent aralkyl, or multivalent 2296-P5WO 89 heteroaralkyl, wherein the multivalent aryl, multivalent heteroaryl, multivalent aralkyl, and multivalent heteroaralkyl are each unsubstituted or substituted with 1, 2, or 3 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{' is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₁ ^{' is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^D ₁ ^{', D} ₂ ^{', and D} ₃ ^{' are independently H, R} _1G ^{, R} _1H ^{, R} _3G ^{, R} _3H ^{, or a protecting group} (e.g., silyl protecting group, substituted silyl protecting group, trialkylsilyl protecting group, silyl ether protecting group, trialkyl silyl ether protecting group, trimethyl silyl ^{ether), wherein R} _1G ^{and R} _1H ^{are as defined above, and wherein R} _3G ^{and R} _3H ^{are as defined} above. It will be appreciated that, although specific embodiments of the disclosure have been described herein for purposes of illustration, various modifications may be made without deviating from the spirit and scope of the disclosure. 2296-P5WO 90 Embodiment 1. A copolymer, comprising a first repeating unit (x) having Formula (I): R_1E

(I) and a second repeating unit (y) having Formula (II):

or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-_X ⁺ _; 2296-P5WO 91 ^R _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{each R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are unsubstituted or substituted with 1, 2, 3, 4, or} ^{5 substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, and cyano;} ^A ₁ ^{and B} ₁ ^{are independently arylene, heteroarylene, aralkylene, or} heteroaralkylene, wherein the arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{and B} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{and K} ₁ ^{are independently a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{and K} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{and K} ₃ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} X⁺ _{is a cation.} Embodiment 2. The copolymer of Embodiment 1, wherein the copolymer has a structure of Formula (III): 2296-P5WO 92 R_1E R_3B y

99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. Embodiment 3. The copolymer of any of the preceding Embodiments, ^{wherein A} ₁ ^{and B} ₁ ^{are independently arylene unsubstituted or substituted with 1, 2, 3, or 4} ^{substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and A} ₂ ^{and B} ₂ ^{are absent.} Embodiment 4. The copolymer of any of the preceding Embodiments, wherein the first repeating unit (x) of Formula (I) is a repeating unit of Formula (I-A):

(I-A), wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and} ^R _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_2A ^{, R} _2B ^{, R} _2C ^{, and R} _2D ^{are independently H, halo, nitro, cyano, aryl, or heteroaryl;} 2296-P5WO 93 ^L ₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected ^{from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} Embodiment 5. The copolymer of any of the preceding Embodiments, wherein the second repeating unit (y) of Formula (II) is a repeating unit of Formula (II-A):

wherein: R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{the R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _4A ^{, R} _4B ^{, R} _4C ^{, and R} _4D ^{are independently H, halo, nitro, cyano, aryl, or heteroaryl;} ^K ₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected ^{from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} 2296-P5WO 94 ^K ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} Embodiment 6. The copolymer of any of the preceding Embodiments, wherein the copolymer has a structure of Formula (IV): R_3b y

(IV), wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%, and wherein: R_1a ^{, R} _1b ^{, R} _1e ^{, and R} _1f ^{are independently SO} ₃ ^{-X+ or H+, provided that at least two} ^{of R} _1a ^{, R} _1b ^{, R} _1e ^{, and R} _1f ^{are SO} ₃ ^{-X+, wherein X+ is independently selected from H+, an} ^{alkali metal ion, a transition metal ion, and [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, and wherein R} _5A ^, ^R _5B ^{, R} _5C ^{, and R} _5D ^{are independently H, C} _1-6 ^{alkyl, aryl, or heteroaryl;} ^R _3a ^{, R} _3b ^{, R} _3e ^{, and R} _3f ^{are independently selected from hydrogen, C} _1-12 ^{alkyl, halo,} phenyl, nitro, and cyano; L₁ ^{and K} ₁ ^{are independently a linking arylene, wherein the arylene is unsubstituted} ^{or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1-6 ^{alkyl, halo,} nitro, cyano, aryl, and heteroaryl; and L₂ ^{, K} ₂ ^{, L} ₃ ^{, and K} ₃ ^{are independently absent or arylene, wherein the arylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} 2296-P5WO 95 Embodiment 7. The copolymer of any of the preceding Embodiments, _{wherein the cation of X} ⁺ _{is selected from H} ⁺ _{, an alkali metal ion, a transition metal ion,} ^{and [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1- ₆ ^{alkyl, aryl, or heteroaryl.} Embodiment 8. The copolymer of any of the preceding Embodiments, ^{wherein L} ₁ ^{and K} ₁ ^{are independently arylene; L} ₂ ^{and K} ₂ ^{are independently absent or} ^{arylene; and L} ₃ ^{and K} ₃ ^{are independently absent or arylene, wherein the arylene are each} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl and halo.} Embodiment 9. The copolymer of any of the preceding Embodiments, ^{wherein L} ₁ ^{and K} ₁ ^{are independently naphthylene, phenylene, or C} _1-6 ^{alkyl-substituted} ^{phenylene; L} ₂ ^{and K} ₂ ^{are independently absent or phenylene; and L} ₃ ^{and K} ₃ ^are independently absent or phenylene, wherein the phenylene are each unsubstituted or ^{substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} ^{alkyl and halo.} Embodiment 10. The copolymer of any of the preceding Embodiments, ^{wherein the L} ₃ ^{, L} ₂ ^{, and L} ₁ ^{of –L} ₃ ^–L ₂ ^–L ₁ ^{–, and the K} ₃ ^{, K} ₂ ^{, and K} ₁ ^{of –K} ₃ ^–K ₂ ^–K ₁ ^{–, are} ,

, , , , , 2296-P5WO 96 , , , and . Embodiment 11. The copolymer of any of the preceding Embodiments, wherein the first repeating unit (x) is selected from: 2296-P5WO 97 _SO + + 3 ^X _SO3 ^X ,

, and any combination thereof, w_{herein X} ⁺ _{is H} ⁺ _{, an alkali metal ion, a transition metal ion, or} ^[N(R _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1-6 ^alkyl, aryl, or heteroaryl. Embodiment 12. The copolymer of any of the preceding Embodiments, wherein the second repeating unit (y) is selected from: 2296-P5WO 98

nd an Embodiment 13. The copolymer of any of the preceding Embodiments, comprising: a first repeating unit (x) selected from 2296-P5WO 99 _SO ^X+ _SO + 3₃ ^X

, and a_{ny combination thereof, wherein X} ⁺ _{is H} ⁺ _{, an alkali metal ion, a transition metal} ^{ion, or [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1- ₆ ^{alkyl, aryl, or heteroaryl; and} a second repeating unit (y) selected from 2296-P5WO 100

, and any combination thereof; wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. Embodiment 14. The copolymer of any of the preceding Embodiments, ^{further comprising a multivalent linker M} ₁ ^{, wherein M} ₁ ^{is bound through a covalent bond} to at least 3 sulfonated polyphenylene repeat units (x) of Formula (I), hydrophobic polyphenylene repeat units (y) of Formula (II), or a combination thereof, wherein the ^{multivalent linker M} ₁ ^{is selected from the group consisting of:}

, _{, ,} ^N _{, , , and .} Embodiment 15. The copolymer of Embodiment 14, wherein the ionomeric polymer has a branched structure of Formula (V): 2296-P5WO 101 R_1E

w^{herein P} ₁ ^{and P} ₂ ^{are independently selected from a repeat unit (x) of Formula (I)} and a repeat unit (y) of Formula (II). Embodiment 16. The copolymer of Embodiment 15, wherein the ratio of ^z/(x+P ₁ ^+P ₂ ^{) is less than 0.2.} Embodiment 17. The copolymer of any of the preceding Embodiments, wherein the mole percent of the first repeating unit (x) is about 85% to about 99%, and the mole percent of the second repeating unit (y) is about 15% to about 1%. Embodiment 18. The copolymer of any of the preceding Embodiments, wherein the mole percent of the first repeating unit (x) is about 90%, and the mole percent of the second repeating unit (y) is about 10%. Embodiment 19. The copolymer of Embodiments 1-18, wherein the copolymer is linear. Embodiment 20. The copolymer of Embodiments 1-18, wherein the copolymer is branched. Embodiment 21. The copolymer of any of the preceding Embodiments, wherein the copolymer is a random copolymer comprising a random distribution of x and y. Embodiment 22. The copolymer of Embodiments 1-20, wherein the copolymer is a statistical copolymer comprising an average composition ratio of (x) and (y). 2296-P5WO 102 Embodiment 23. The copolymer of Embodiments 1-20, wherein the copolymer is a random block copolymer, comprising: a first block selected from a first repeating unit (x): SO₃ X+ SO + 3 X ,

, , a_{nd any combination thereof, wherein X} ⁺ _{is H} ⁺ _{, an alkali metal ion, a transition metal ion,} o^{r [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1- ₆ ^{alkyl, aryl, or heteroaryl; and} a second block selected from the second repeating unit (y): 2296-P5WO 103 , m , and any combination thereof, wherein: n is an integer of from 3 to 100, m is an integer of from 3 to 100; and wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. Embodiment 24. A method of making a random copolymer, comprising forming a mixture of a first repeating unit (x) of Formula (VI): A

(VI) wherein: 2296-P5WO 104 ^R _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from _{C1-6 alkyl, halo, phenyl, nitro, cyano, SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _{, and provided that} ^{at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl} _{substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and}

_COO-_X ⁺ _; A₁ ^{is independently arylene, heteroarylene, aralkylene, or heteroaralkylene, each} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{is independently absent, arylene, or heteroarylene, wherein the arylene and} heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{is independently a linking heteroatom, arylene, heteroarylene, aralkylene, or} heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is independently absent, arylene, or heteroarylene, wherein the arylene and} heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{is independently absent, arylene, or heteroarylene, wherein the arylene and} heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} X⁺ _{is H} ⁺ _{or a cation; and} A is a reactive first terminal group, and a second repeating unit (y) of Formula (VII): 2296-P5WO 105 R_3E B wherein

R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, each} unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from ^C _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, and cyano;} ^B ₁ ^{is independently arylene, heteroarylene, aralkylene, or heteroaralkylene, each} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, B₂ ^{is independently absent, arylene, or heteroarylene, wherein the arylene and} heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; K₁ ^{is independently a linking heteroatom, arylene, heteroarylene, aralkylene, or} heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₂ ^{is independently absent, arylene, or heteroarylene, wherein the arylene and} heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₃ ^{is independently absent, arylene, or heteroarylene, wherein the arylene and} heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} B is a second reactive terminal group configured to react with A, and reacting A and B to provide a random copolymer of Formula (III): 2296-P5WO 106 R_1E R_3B y

, wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. Embodiment 25. A membrane or ionomer comprising a copolymer of any of Embodiments 1-23. Embodiment 26. An ionomeric copolymer membrane, comprising a copolymer of any of Embodiments 1-23, wherein the ionomeric copolymer membrane has an IEC of 2.4 – 3.5 meq/g. Embodiment 27. An ionomeric copolymer membrane, comprising a copolymer of any of Embodiments 1-23, wherein the ionomeric copolymer membrane exhibits a water uptake of 60 – 120 wt% at room temperature. 2296-P5WO 107

Claims

CLAIMS The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows: 1. A copolymer, comprising a first repeating unit (x) having Formula (I): R_1E

(I) and a second repeating unit (y) having Formula (II):

wherein the copolymer comprises: a mole percent of (x) of about 75% to about 99%, a mole percent of (y) of about 25% to about 1%, and wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and} ^R _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents 2296-P5WO 108 ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-_X ⁺ _; R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{each R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{is unsubstituted or substituted with 1, 2, 3, 4, or 5} ^{substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, and cyano;} ^A ₁ ^{and B} ₁ ^{are independently arylene, heteroarylene, aralkylene, or} heteroaralkylene, wherein the arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{and B} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{and K} ₁ ^{are independently a linking heteroatom, arylene, heteroarylene,} aralkylene, or heteroaralkylene, wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{and K} ₂ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{and K} ₃ ^{are independently absent, arylene, or heteroarylene, wherein the arylene} and heteroarylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} X⁺ _{is a cation.} 2. The copolymer of Claim 1, wherein the copolymer has a structure of Formula (III): 2296-P5WO 109 R_1E R_3B y

99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. 3^{. The copolymer of Claim 1, wherein A} ₁ ^{and B} ₁ ^{are independently arylene,} wherein the arylene is unsubstituted or substituted with 1, 2, 3, or 4 substituents ^{independently selected from halo, nitro, cyano, aryl, and heteroaryl; and A} ₂ ^{and B} ₂ ^are absent. 4. The copolymer of Claim 1, wherein the first repeating unit (x) of Formula (I) is a repeating unit of Formula (I-A):

(I-A), wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and} ^R _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_2A ^{, R} _2B ^{, R} _2C ^{, and R} _2D ^{are independently H, halo, nitro, cyano, aryl, or heteroaryl;} 2296-P5WO 110 ^L ₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected ^{from C} _{1- 6} ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} 5. The copolymer of Claim 1, wherein the second repeating unit (y) of Formula (II) is a repeating unit of

, wherein: R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^,

^R _3F ^{are independently aryl or heteroaryl, wherein} ^{the R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} ^R _4A ^{, R} _4B ^{, R} _4C ^{, and R} _4D ^{are independently H, halo, nitro, cyano, aryl, or heteroaryl;} ^K ₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} 2296-P5WO 111 ^K ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} 6. The copolymer of Claim 1, wherein the copolymer has a structure of Formula (IV): R_3b y

(IV), wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%, and wherein: R_1a ^{, R} _1b ^{, R} _1e ^{, and R} _1f ^{are independently SO} ₃ ^{-X+ or H+, provided that at least two} ^{of R} _1a ^{, R} _1b ^{, R} _1e ^{, and R} _1f ^{are SO} ₃ ^{-X+, wherein X+ is independently selected from H+, an} ^{alkali metal ion, a transition metal ion, and [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, and wherein R} _5A ^, ^R _5B ^{, R} _5C ^{, and R} _5D ^{are independently H, C} _1-6 ^{alkyl, aryl, or heteroaryl;} ^R _3a ^{, R} _3b ^{, R} _3e ^{, and R} _3f ^{are independently selected from hydrogen, C} _1-12 ^{alkyl, halo,} phenyl, nitro, and cyano; L₁ ^{and K} ₁ ^{are independently a linking arylene, wherein the arylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl; and} ^L ₂ ^{, K} ₂ ^{, L} ₃ ^{, and K} ₃ ^{are independently absent or arylene, wherein the arylene are} each unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _{1- 6} ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl.} 2296-P5WO 112

_{7. The copolymer of Claim 1, wherein the cation of X} ⁺ _{is selected from H} ⁺ _, ^{an alkali metal ion, a transition metal ion, and [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^, ^R _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1-6 ^{alkyl, aryl, or heteroaryl.} ^{8. The copolymer of Claim 1, wherein L} ₁ ^{and K} ₁ ^{are independently arylene;} ^L ₂ ^{and K} ₂ ^{are independently absent or arylene; and L} ₃ ^{and K} ₃ ^{are independently absent or} arylene, wherein the arylene are each unsubstituted or substituted with 1, 2, 3, or 4 ^{substituents independently selected from C} _1-6 ^{alkyl and halo.} ^{9. The copolymer of Claim 1, wherein L} ₁ ^{and K} ₁ ^{are independently} ^{naphthylene or phenylene; L} ₂ ^{and K} ₂ ^{are independently absent or phenylene; and L} ₃ ^and ^K ₃ ^{are independently absent or phenylene, wherein the phenylene are each unsubstituted} ^{or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} ^{alkyl and} halo. 1^{0. The copolymer of Claim 1, wherein the L} ₃ ^{, L} ₂ ^{, and L} ₁ ^{of –L} ₃ ^–L ₂ ^–L ₁ ^{–, and} ^{the K} ₃ ^{, K} ₂ ^{, and K} ₁ ^{of –K} ₃ ^–K ₂ ^–K ₁ ^{–, are each independently selected from} ,

, , , 2296-P5WO 113 , . 5 11. The copolymer of Claim 1, wherein the first repeating unit (x) is selected from: 2296-P5WO 114 _SO ^X+ _SO ^X+ 3₃ ,

, and any combination thereof, w_{herein X} ⁺ _{is H} ⁺ _{, an alkali metal ion, a transition metal ion, or} ^[N(R _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1-6 ^alkyl, aryl, or heteroaryl. 12. The copolymer of Claim 1, wherein the second repeating unit (y) is selected from: 2296-P5WO 115

nd an 13. The copolymer of Claim 1, comprising: a first repeating unit (x) selected from 2296-P5WO 116 _SO ^X+ _S + 3_O3 ^X

, , 2296-P5WO 117

, and any combination thereof, wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. 1^{4. The copolymer of Claim 1, further comprising a multivalent linker M} ₁ ^, ^{wherein M} ₁ ^{is bound through a covalent bond to at least 3 sulfonated polyphenylene repeat} units (x) of Formula (I), hydrophobic polyphenylene repeat units (y) of Formula (II), or a c^{ombination thereof, wherein the multivalent linker M} ₁ ^{is selected from the group} consisting of:

, _{, , , , , .} 15. The copolymer of Claim 14, wherein the ionomeric polymer has a branched structure of

P₂ (V), 2296-P5WO 118 ^{wherein P} ₁ ^{and P} ₂ ^{are independently selected from a repeat unit (x) of Formula (I)} and a repeat unit (y) of Formula (II). 1^{6. The copolymer of Claim 15, wherein the ratio of z/(x+P} ₁ ^+P ₂ ^{) is less than} 0.2. 17. The copolymer of Claim 1, wherein the mole percent of the first repeating unit (x) is about 85% to about 99%, and the mole percent of the second repeating unit (y) is about 15% to about 1%. 18. The copolymer of Claim 1, wherein the mole percent of the first repeating unit (x) is about 90%, and the mole percent of the second repeating unit (y) is about 10%. 19. The copolymer of Claim 1, wherein the copolymer is linear. 20. The copolymer of Claim 1, wherein the copolymer is branched. 21. The copolymer of Claim 1, wherein the copolymer is a random copolymer comprising a random distribution of (x) and (y). 22. The copolymer of Claim 1, wherein the copolymer is a statistical copolymer comprising an average composition ratio of (x) and (y). 23. The copolymer of Claim 1, wherein the copolymer is a random block copolymer, comprising: a first block selected from a first repeating unit (x): 2296-P5WO 119 _SO ^X+ _S + 3_O3 ^X

, _{and any combination thereof, wherein X} ⁺ _{is H} ⁺ _{, an alkali metal ion, a transition metal ion,} ^{or [N(R} _5A ^)(R _5B ^)(R _5C ^)(R _5D ^{)]+, wherein R} _5A ^{, R} _5B ^{, R} _5C ^{, R} _5D ^{are independently H, C} _1- ₆ ^{alkyl, aryl, or heteroaryl; and} a m

, , 2296-P5WO 120 m , and any combination thereof, wherein: n is an integer of from 3 to 100, m is an integer of from 3 to 100; and wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. 24. A method of making a random copolymer, comprising forming a mixture of a first repeating unit (x) of Formula (VI):

wherein: R_1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are independently aryl or heteroaryl, wherein} ^{the R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^{, and R} _1F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃- ^{X+, PO} ₃ ^2-X+ ₂ ^{, and COO-X+, and provided that at least two of R} _1A ^{, R} _1B ^{, R} _1C ^{, R} _1D ^{, R} _1E ^, ^{and R} _1F ^{are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents} _{independently selected from SO3}-_X ⁺ _{, PO3} ^2- _X ⁺ _{2, and COO}-_X ⁺ _; R_1G ^{and R} _1H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents 2296-P5WO 121 ^{independently selected from C} _1-6 ^{alkyl, halo, phenyl, nitro, cyano, SO} ₃ ^{-X+, PO} ₃ ^2-X+ ₂ ^{, and} _COO-_X ⁺ _; A₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^L ₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _1- ₆ ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} X⁺ _{is a cation; and} A is a reactive first terminal group, and a second repeating unit (y) of Formula (VII): B

(VII) wherein R_3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are independently aryl or heteroaryl, wherein} ^{the R} _3A ^{, R} _3B ^{, R} _3C ^{, R} _3D ^{, R} _3E ^{, and R} _3F ^{are each unsubstituted or substituted with 1, 2, 3, 4,} ^{or 5 substituents independently selected from C} _1-12 ^{alkyl, halo, phenyl, nitro, and cyano;} 2296-P5WO 122 ^R _3G ^{and R} _3H ^{are independently H, aryl, or heteroaryl, wherein the aryl and} heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents ^{independently selected from C} _1-6 ^{alkyl, halo, nitro, and cyano;} ^B ₁ ^{is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein the arylene,} heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, B₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; K₁ ^{is a linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene,} wherein the linking heteroatom, arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from ^C _1-6 ^{alkyl, halo, nitro, cyano, aryl, and heteroaryl;} ^K ₂ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; K₃ ^{is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are} ^{unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C} _{1- 6} alkyl, halo, nitro, cyano, aryl, and heteroaryl; and B is a second reactive terminal group configured to react with A, and reacting A and B to provide a random copolymer of Formula (III):

y R_3E (III), wherein the mole percent of the first repeating unit (x) is about 75% to about 99%, and the mole percent of the second repeating unit (y) is about 25% to about 1%. 2296-P5WO 123

25. A membrane or ionomer comprising a copolymer of any one of Claims 1- 23. 26. An ionomeric copolymer membrane, comprising a copolymer of any one of Claims 1-23, wherein the ionomeric copolymer membrane has an IEC of 2.4 – 3.5 meq/g. 27. An ionomeric copolymer membrane, comprising a copolymer of any one of Claims 1-23, wherein the ionomeric copolymer membrane exhibits a water uptake of 60 – 120 wt% at room temperature. 28. An electrochemical device comprising the copolymer membrane of Claim 25, wherein the electrochemical device is a fuel cell, electrolyzer, hydrogen pump, thermoelectrochemical hydrogen pump, electrochemical hydrogen compressor, redox flow battery, or other electrochemical device. 2296-P5WO 124