Zwitterionic compounds and polymers

Abstract

This invention provides zwitterionic compounds and polymers. The zwitterionic compounds and polymers have applications in soft robotics as actuators, in electronics as circuit components, and in energy storage as an electrolyte.

Description

[0001] ZWITTERIONIC COMPOUNDS AND POLYMERS

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0003] This invention was made with government support under 2011754 and 2025158 awarded by National Science Foundation (NSF). The government has certain rights in this invention.

[0004] BACKGROUND

[0005] The advent of soft, electroactive materials has opened new avenues for compliant iontronics and electronics, with envisioned applications spanning wearable and implantable devices, e-skins, and soft robotic actuators and grippers. Among these, soft dielectrics, capable of strong polarization in an electric field, are critical; while precise property requirements vary by application, they are unified in the need for mechanical compliance and excellent electronic properties. Presently, few materials offer both compliance and polarizability, necessitating compromises in device design. Current implantable bioelectronic sensors mechanically mismatch the surrounding tissue while dielectric actuators employ liquids (e.g., vegetable oil) or silicone elastomers with low dielectric constants ( ~ 2-5) that necessitate kilovolt-scale working potentials. This limited materials palette limits the utility of these potentially transformative devices.

[0006] Permanent dipoles in a soft medium offer a promising platform to realize high-permittivity dielectrics. Both polar small molecules and tethered dipoles in an elastomer align in an electric field to effect bulk polarization. Zwitterions, which consist of oppositely charged ions separated by a covalent spacer, exhibit superlative dipole moments for two reasons. First, each pole carries a full charge (cation, anion), affording larger polarization amplitude compared to electronegativity- and delocalization-mediated dipoles. Second, ZIs can be prepared with inter-charge spacers that are several atoms in length that enable longer dipoles and, thus, higher ft.

[0007] Despite their promise, most ZIs suffer from important limitations. First, they possess high Tm, typically above 200°C. This poses a challenge as their arrested states ( / .e., crystal, glass) prevent field-mediated alignment and bulk polarization and, hence, do not amplify permittivity. Moreover, these arrested phases are stiff, undermining their mechanical compliance. Second, zwitterionic liquids reported to date are extremely viscous. Higher viscosity increases dielectric relaxation timescales and damps mechanical movement, limiting practical utility at room temperature. Hence, new zwitterions, e.g., that are liquid at room temperature and exhibit dramatically decreased viscosity, are needed.

[0008] SUMMARY

[0009] The present invention provides zwitterionic compounds and polymers. The compounds and polymers can be utilized as dielectrics in applications such as dielectric actuators, capacitors, and field effect transistors.

[0010] In one aspect, the invention provides a compound of formula:

[0011] Ry-Y-Rb-X-Rx, wherein X is a negatively charged functional group, Y is a positively charged functional group, Rb is a linker of at least 3 atoms long, RY is a C>1 hydrocarbyl or a C>1 heterohydrocarbyl, and Rx is absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl. In some embodiments, X includes a negatively charged N or B atom. In some embodiments, Rb is a linker of at least 5 atoms long. In some embodiments, Rb is a C>1 heterohydrocarbylene. In some embodiments, RY is a C>5 heterohydrocarbyl.

[0012] In some embodiments, X includes:

[0013] In some embodiments, Y includes an optionally substituted positively charged five- or six-membered nitrogen containing heterocyclylene.

[0014] In some embodiments, Rb includes a C>3 hydrocarbylene or a C>3 heterohydrocarbylene. In some embodiments, Rb includes an ether, polyether, thioether, or polythioether. In some embodiments, Rb includes polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane. In some embodiments, Rb includes a polymer with a molecular weight between 100 g / mol and 1 ,000,000 g / mol.

[0015] In some embodiments, Rx includes a C>1 hydrocarbyl or C>1 heterohydrocarbyl. In some embodiments, Rx includes an ether, polyether, thioether, or polythioether. In some embodiments, Rx includes a terminal reactive group, e.g., a polymerizable group. In some embodiments, the terminal reactive group includes an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone.

[0016] In some embodiments, RY includes a C>1 hydrocarbyl or C>1 heterohydrocarbyl. In some embodiments, RY includes an ether, polyether, thioether, or polythioether. In some embodiments, RY includes a terminal reactive group, e.g., a polymerizable group. In some embodiments, the terminal reactive group includes an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone. In some embodiments, the compound is a compound of the following table:

[0017]

[0018] , wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000.

[0019] In another aspect, the invention provides a polymer including a backbone including at least two subunits of formula:

[0020] -RA-Z-RB-, wherein each Z is independently a negatively or positively charged functional group, each RA is independently a C>1 hydrocarbylene, C>1 heterohydrocarbylene, or C>1 heterohydrocarbylene, and each RB is independently a C>1 hydrocarbylene, C>1 heterohydrocarbylene, or C>1 heterohydrocarbylene, and wherein the negatively and positively charged functional groups are present in the polymer in a ratio between 4:5 and 5:4.

[0021] In some embodiments, the negatively charged functional group includes some embodiments, the positively charged functional group includes an optionally substituted five- or six-membered nitrogen containing heterocyclylene. In some embodiments, the polymer includes n subunits of the following table: , wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000.

[0022] independently an integer between 1 and 1000.

[0023] In another aspect, the invention provides a polymer including a backbone and at least one pendant group of formula:

[0024] -RY-Y-Rb-X-Rx or -RY-X-Rb-Y-Rx wherein each X is independently a negatively charged functional group, each Y is independently a positively charged functional group, each Rb is independently a linker of at least 3 atoms long, each RY is independently a C>1 hydrocarbylene or a C>1 heterohydrocarbylene, and each Rx is independently absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl.

[0025] In some embodiments, the backbone of the polymer includes polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane. In some embodiments, X includes a negatively charged N or B atom. In some embodiments, Rb is a linker of at least 5 atoms long. In some embodiments, Rb is C>1 heterohydrocarbylene. In some embodiments, RY is C>5 heterohydrocarbyl. In some embodiments, the polymeric compound further includes a second pendant group including a linking moiety. In some embodiments, the linking moiety is a thiol.

[0026] In some embodiments, the polymer has any of the following formulas: wherein n, a, b, and c are integers from 10-1000, and R is heterohydrocarbyl, e.g., polyethylene glycol, hydrocarbyl, aryl, heteroaryl, cycloalkyl, polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane. In some embodiments, the pendant group is: , wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000.

[0027] In some embodiments, the polymer includes: , wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000.

[0028] In another aspect, the invention provides a polymer including a backbone and at least two pendant groups of the formula: -RA-Z-RB, wherein each Z is independently a negatively or positively charged functional group, each RA is independently a C>1 hydrocarbylene or a C>1 heterohydrocarbylene, and each RB is independently absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl, wherein the negatively and positively charged functional groups are present in the polymer in a ratio between 4:5 and 5:4. In some embodiments, the backbone of the polymer includes polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane.

[0029] In some embodiments, the negatively charged functional group includes:

[0030] In some embodiments, the positively charged functional group includes an optionally substituted five- or six-membered nitrogen containing heterocyclylene.

[0031] In some embodiments, one of the pendant groups is of the following table:

[0032] independently an integer between 1 and 1000, and wherein r is an integer between 0 and 10.

[0033] In some embodiments, the polymer includes a polymer of the following table:

[0034] wherein R includes a monofunctional or difunctional RAFT agent, such a , wherein m is an integer between 0 and 19, and n, p, q, and r are independently an integer between 1 and 1000.

[0035] In another aspect, the invention provides a block copolymer including any polymer described herein.

[0036] In another aspect, the invention provides a cross-linked polymer including any polymer described herein.

[0037] In one aspect, the invention provides a dielectric actuator including two electrodes and a dielectric material including a compound or polymer described herein in contact with and separating the two electrodes, wherein, when a voltage is applied to the two electrodes, the dielectric material polarizes in response to the applied electric field generated between the two electrodes to produce a strain.

[0038] In one aspect, the invention provides a capacitor including two electrodes and a dielectric material including a compound or polymer described herein in contact with and separating the two electrodes, wherein, when a voltage is applied to the two electrodes, the dielectric material polarizes in response to the applied electric field generated between the two electrodes to store electrical energy.

[0039] In one aspect, the invention provides a transistor including a source, gate, and drain terminals and a gate dielectric including a compound or polymer described herein.

[0040] In one aspect, the invention provides a hydraulically amplified self-healing electrostatic (HASEL) actuator including two electrodes and a dielectric material including a compound as described herein enclosed inside an elastic shell that is in contact with and separating the two electrodes, wherein, when a voltage is applied to the two electrodes, the enclosed compound polarizes to effect actuation.

[0041] In one aspect, the invention provides a battery including an anode and a cathode and a solid-state electrolyte including a compound or polymer described herein disposed between the anode and the cathode.

[0042] In one aspect, the invention provides a battery including an anode and a cathode and a gel-phase electrolyte including a compound or polymer described herein disposed between the anode and the cathode.

[0043] For any compound or polymer described herein, acidic and basic moieties may be protonated or deprotonated depending on the pH. The disclosure encompasses free acid, free base, cationic, anionic, zwitterionic, and salt forms. Furthermore, any polymer depicted herein as statistical or block may alternatively be block or statistical.

[0044] Definitions

[0045] To facilitate the understanding of this invention, a number of terms are defined below and throughout the disclosure. 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 to which this invention belongs. The terminology herein is used to describe specific embodiments of the invention, but their usage does not limit the invention, except as outlined in the claims.

[0046] By the suffix “-ene,” as used herein is meant a divalent form of the group to which the suffix is appended.

[0047] By “hydrocarbyl,” as used herein, is meant a branched, unbranched, acyclic group including the elements C and H. For example, hydrocarbyl groups can include alkyl (saturated), alkenyl (unsaturated with at least one carbon double bond and no carbon triple bonds), and alkynyl (unsaturated with at least one carbon triple bond). Examples include methyl, ethyl, propylene, butyl, pentyl, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene, heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene, hexacosylene, heptacosylene, octacosylene, nonacosylene, or triacontylene, and the like. Hydrocarbyl groups may be unsubstituted or substituted with one or more substituents. Hydrocarbyl groups include 1 or more carbon atoms, e.g., e.g., 1-30, such as 1 to 10, 2 to 10, 3 to 10, 5 to 20, or 8-20 in the main chain.

[0048] The term “alkenyl,” as used herein, refers to an acyclic straight or branched chain monovalent hydrocarbon group containing one or more double bonds, no triple bonds, and from 2 to 12 (e.g., 2 to 6) carbons, unless otherwise specified. Alkenyl groups may be substituted or unsubstituted. Exemplary substituents include alkoxy, sulfide, amido, amino, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heterocyclyl, hydroxyl, oxo, and thiol.

[0049] The term “alkyl,” as used herein, refers to an acyclic straight or branched chain, saturated, monovalent hydrocarbon group having from 1 to 12 carbons (e.g., 1 to 6), unless otherwise specified. Alkyl groups may be substituted or unsubstituted. Exemplary substituents include alkoxy, sulfide, amido, amino, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heterocyclyl, hydroxyl, oxo, and thiol. An alkyl may be substituted with an oxo to form an aldehyde or ketone.

[0050] The term “alkynyl,” as used herein, refers to a straight or branched monovalent hydrocarbon group containing one or more triple bonds and from 2 to 12 (e.g., 2 to 6) carbons, unless otherwise specified. Alkynyl groups may be unsubstituted or substituted as alkenyl groups. Exemplary substituents include alkoxy, sulfide, amido, amino, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heterocyclyl, hydroxyl, oxo, and thiol.

[0051] By “heterohydrocarbyl,” as used herein, is meant a hydrocarbyl group in which at least one carbon atom in the main chain is replaced with a heteroatom, e.g., O, S, or N, along a length of or at a terminus of the chain of carbons. Exemplary substituents include alkenyl, alkynyl, alkoxy, sulfide, amido, amino, aryl, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heterocyclyl, hydroxyl, oxo, phospho, and thiol. Examples include mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, or decaethylene glycol and the thioether equivalents. Heterohydrocarbyl groups may be unsubstituted or substituted with one or more substituents. Heterohydrocarbyl groups include 1 or more carbon atoms and 1 or more heteroatoms, e.g., 1-30, such as 1 to 10, 2 to 10, 3 to 10, 5 to 20, or 8-20 in the main chain. Exemplary number of heteroatoms are 1 to 10.

[0052] The term “alkoxy,” as used herein, refers to a group of the formula -OR, where R is alkyl. The term “amido,” as used herein, refers to a group of the formula — C(=O)NRGRH, where each of RGand RHare independently H, alkyl, alkenyl, alkynyl, cycloalkyl, heteroalkyl, heterocyclyl, or aryl.

[0053] The term “amino,” as used herein, refers to a group of formula — NRGRHor — NRGRHR', where each of RG, RH, and R1is independently H, alkyl, alkenyl, alkynyl, cycloalkyl, heteroalkyl, heterocyclyl, or aryl.

[0054] The term “aryl,” as used herein, refers to any monocyclic or fused ring bicyclic or multicyclic system containing only carbon atoms in the ring(s), which has the characteristics of aromaticity in terms of electron distribution throughout the ring system, e.g., phenyl, naphthyl, or phenanthryl. An aryl group may have, e.g., six to sixteen carbons (e.g., six carbons, ten carbons, thirteen carbons, fourteen carbons, or sixteen carbons). Aryl groups may be unsubstituted or substituted. Exemplary substituents include alkyl, alkenyl, alkynyl, alkoxy, sulfide, amido, amino, aryl, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heteroalkyl, heterocyclyl, hydroxyl, and thiol.

[0055] The term "acyl,” as used herein, refers to a group having the general formula -C(=O)RJ, wherein RJis hydrogen, alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, or aryl.

[0056] R1C DR2

[0057] The term “acetal,” as used herein, refers to R3R4, where each of R1, R2, R3, and R4are independently H, alkyl, alkenyl, alkynyl, cycloalkyl, heteroalkyl, heterocyclyl, or aryl.

[0058] The term “dibenzocyclooctyne,” as used herein, refers

[0059] The term “carbonate,” as used herein, refers to a group of the formula — OC(=O)OR, wherein R is H, alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, or aryl.

[0060] The term “carbamate,” as used herein, refers to a group of the formula — OC(=O)NRGRH, where each of RGand RHare independently H, alkyl, alkenyl, alkynyl, cycloalkyl, heteroalkyl, heterocyclyl, or aryl

[0061] The term “carboxyl,” as used herein, refers to a group of the formula — (C=O)OH. A carboxy group may be esterified or amidated. For esters, the H atom is replaced with alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, or aryl, and for amides, the -OH moiety is replaced with amino.

[0062] The term “cyano,” as used herein, refers to — C=N.

[0063] The term “cycloalkyl,” as used herein, refers to a cyclic, saturated, monovalent hydrocarbon group having from 3 to 12 carbons (e.g., 3 to 6), unless otherwise specified. Cycloalkyl groups may be substituted or unsubstituted. Exemplary substituents include alkyl, alkenyl, alkynyl, alkoxy, sulfide, amido, amino, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heterocyclyl, hydroxyl, oxo, and thiol. The term “ether,” as used herein, refers to RG— O — RH, where each of RGand RHare independently alkyl, alkenyl, alky ny I, cycloalkyl, heteroalkyl, heterocyclyl, or aryl.

[0064] The term “epoxy,” as used herein, refers to >0, where the oxygen is bound to adjacent carbon atoms.

[0065] The term “ester,” as used herein, refers to a group having the general formula -C(=0)0RJ, wherein RJis alkyl, heteroalkyl, alkenyl, alky ny I, heterocyclyl, or aryl. An exemplary ester is N-hydroxysuccinimide ester.

[0066] The term “halo,” as used herein, refers to a F, Cl, Br, or I radical.

[0067] The term “heteroaryl,” as used herein, refers to an aromatic heterocyclyl group. For example, a single ring heteroaryl group includes pyridyl; fused ring heteroaryl groups include benzimidazolyl, quinolinyl, acridinyl; and a non-fused bi-heteroaryl group includes bipyridinyl. Further examples of heteroaryls include, but are not limited to, furanyl, thienyl, oxazolyl, acridinyl, phenazinyl, benzimidazolyl, benzofuranyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzothiophenyl, benzoxadiazolyl, benzotriazolyl, imidazolyl, indolyl, isoxazolyl, isoquinolinyl, indolizinyl, isothiazolyl, isoindolyloxadiazolyl, indazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl, pyrrolyl, pyrazinyl, pyrazolyl, purinyl, phthalazinyl, pteridinyl, quinolinyl, quinazolinyl, quinoxalinyl, triazolyl, tetrazolyl, thiazolyl, triazinyl, thiadiazolyl and the like. Heteroaryl groups may be substituted or unsubstituted. Exemplary substituents include alkyl, alkenyl, alkynyl, alkoxy, sulfide, amido, amino, aryl, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heterocyclyl, hydroxyl, and thiol.

[0068] The term “heterocyclyl,” as used herein, represents a monovalent, monocyclic or fused ring bicyclic or multicyclic system having at least one heteroatom as a ring atom. For example, a heterocyclyl group may have, e.g., one to fifteen carbon ring atoms (e.g., a C1-C2, C1-C3, C1-C4, C1-C5, Ci-Ce, C1-C7, Ci-Ca, C1- C9, C1-C10, C1-C11 , C1-C12, C1-C13, C1-C14, or C1-C15 heterocyclyl) and one or more (e.g., one, two, three, four, or five) ring heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur. Heterocyclyl groups may or may not include a ring that is aromatic. Heterocyclyl groups may be unsubstituted or substituted. In preferred embodiments of the invention, a heterocyclyl group is a 3- to 8- membered ring, a 3- to 6-membered ring, a 4- to 6-membered ring, a 5-membered ring, or a 6-membered ring. Exemplary 5-membered heterocyclyl groups may have zero to two double bonds, and exemplary 6- membered heterocyclyl groups may have zero to three double bonds. The term “basic nitrogen containing heterocycle,” as used herein, refers to a heterocyclyl group having at least one ring nitrogen (e.g., 1 to 4 nitrogen atoms, e.g., 1 or 2) that can accept a proton from solution, e.g., imidazolyl or benzimidazolyl. Heterocyclyl groups may be substituted or unsubstituted. Exemplary substituents include alkyl, alkenyl, alkynyl, alkoxy, sulfide, amido, amino, aryl, carbonate, carboxyl, cyano, cycloalkyl, epoxy, halo, heteroalkyl, heterocyclyl, hydroxyl, and thiol.

[0069] The term “imide,” as used herein, refers t each of R1and R2are independently H, alkyl, alkenyl, alkynyl, cycloalkyl, heteroalkyl, heterocyclyl, or aryl. The term “oxo,” as used herein, refers to =0.

[0070] The term “phospho,” as used herein refers to — P(=O)(ORK)2, wherein each RKis hydrogen, alkyl, alkenyl, alky nyl, heteroalkyl, cycloalkyl, aryl, or heterocyclyl, e.g., heteroaryl.

[0071] The term “sulfide,” as used herein refers to — SRM, wherein RMis alkyl, alkenyl, alky nyl, heteroalkyl, cycloalkyl, aryl, or heterocyclyl, e.g., heteroaryl.

[0072] The term “disulfide,” as used herein refers to — S — S — RG, where RGis independently alkyl, alkenyl, alky nyl, cycloalkyl, heteroalkyl, heterocyclyl, or aryl.

[0073] The term “thiol,” as used herein, refers to — SH.

[0074] The term “thioether,” as used herein, refers to — S — RG, where RGis alkyl, alkenyl, alky nyl, cycloalkyl, heteroalkyl, heterocyclyl, or aryl.

[0075] The term “main chain,” as used herein, refers to the longest linear sequence of atoms between two termini of a group. For example, a propyl group has three atoms in the main chain, while an isopropyl group has two atoms in the main chain. The length of a linker, as used herein, is the number of atoms in the main chain of the linker.

[0076] The notation showing a double line through a chemical bond between two polymers, e.g., as usec| herein, refers to a statistical polymer, as opposed to a block copolymer, indicating that the two polymers are statistically distributed along the length of the chain as one heterogeneous polymer with statistical alternation between the two types. If more than two polymers are represented with double lines between the polymers, the more than two polymers are statistically distributed along the length of the chain.

[0077] The term “RAFT agent,” as used herein, refers to a compound that reacts with an active site of a polymer where the polymer is growing, e.g., a thiocarbonylthio compound (e.g., a dithioester, thiocarbamate, or xanthate), and bonds to the polymer, leaving behind a reactive product that facilitates further polymerization.

[0078] Substituents for hydrocarbyl, heterohydrocarbyl, and heterocyclyl groups described herein include halo (e.g., fluoro, chloro, bromo, or iodo, including perhalo such as perfluoro), hydroxyl (OH), thiol (SH), carboxyl (COOH), oxo (=0), or a polymerizable group, as described herein. Linear groups may also be substituted with heterocyclyl, and heterocyclyl may be substituted with hydrocarbyl or heterohydrocarbyl.

[0079] BRIEF DESCRIPTION OF THE DRAWINGS

[0080] FIG. 1 A shows examples of zwitterionic liquids as a dielectric material where the zwitterionic liquid itself is the dielectric material. FIG. 1 B shows an example of zwitterionic liquids as a dielectric material where the zwitterionic liquid molecule is linked to linear or network polymers.

[0081] FIG. 2 shows the differential scanning calorimetry curves for four zwitterionic liquids.

[0082] FIG. 3 shows the dielectric spectra of three exemplary zwitterionic liquids (the last being a eutectic mixture of two solid molecules). The relative permittivity of the zwitterionic liquid is plotted as a function of frequency, and it is suggested that the number of constituents in the linker influences the frequency dependent dielectric response of the zwitterionic liquid.

[0083] FIG. 4 shows the thermal characterization of compounds of the invention. Tm, Tg(top) and AHm, ASm(bottom). The dashed line represents 20 °C; molecules 1-12 exhibit Tm> 20 °C and reach thermodynamic minima as crystalline solids at room temperature. Molecules 13-18 were isolated as liquids and exhibited no crystallization when cycled to -90 °C at 10 °C min1or when stored at 22 °C in a vacuum desiccator for at least 4 months. Data are represented as mean ± SD, N = 3.

[0084] FIGS. 5A-5D show the impact on Tmof : a) methyl, ethyl, butyl, allyl, and methoxyethoxyethyl imidazolium tail (reference: butyl); b) methyl versus proton at the imidazolium 2 position (reference: methyl); c) 4, 6, 8, and 16-atom inter-charge spacer (reference: 4-carbon spacer); d) sulfonate, CFs-sulfonimide, and C4F9- sulfonimide anion (reference: sulfonate). Data are represented as mean ± SD, N = 3. Modifications of the four positions produce different relative melting temperatures with respect to the reference.

[0085] FIGS. 6A-6D show how the imidazolium tail impacts the melting behavior of zwitterions. Tm, AHm, and ASmof a) imidazolium sulfonates with 4-carbon spacer and butyl, allyl, and MEE tails; b) imidazolium sulfonimides with 4-carbon spacer and methyl, ethyl, butyl, allyl, and MEE tails; c) imidazolium sulfonimides with 4-carbon spacer, a methyl group at C2, and butyl and MEE tails; d) imidazolium sulfonimides with 6-carbon spacer and butyl and MEE tails. Data are represented as mean ± SD, N = 3. ns not synthesized.

[0086] FIGS. 7A-7B show how substitution at the imidazolium 2 position impacts melting behavior of zwitterions. Tm, AHm, and ASmof imidazolium sulfonimides with 4-carbon spacer and a) butyl tail and methyl versus hydrogen substitution at the imidazolium C2 position; b) MEE tail and methyl versus hydrogen substitution at the imidazolium C2 position. Data are represented as mean ± SD, N = 3. ns not synthesized.

[0087] FIGS. 8A-8D show how the spacer length influences Tgand ACgin zwitterionic liquids, a) Tgas a function of spacer length for three zwitterion classes with Rt = allyl, butyl, and MEE; change in b) specific ( lCgs) and c) molar (ztCg,m) heat capacity jump at Tgas a function of spacer length, and d) (ACgm) as a function of Tgfor the same ten molecules.

[0088] FIGS. 9A-9C show how intercharge spacer Rsimpacts melting behavior of zwitterions. Tm, AHm, and ASmof imidazolium sulfonimides with a) an allyl tail and 4- versus 16-atom spacer; b) a butyl tail and 4, 6, 8, and 16-atom spacers; c) a MEE tail and 4, 6, 8, and 16-atom spacers. Data are represented as mean ± SD, N = 3. ns not synthesized. FIGS. 10A-10C show how anion composition Raimpacts melting behavior of zwitterions. Tm, AHm, and ASmof zwitterions composed of imidazolium cations with 4-carbon inter-charge spacer, a) an allyl tail and sulfonate, CFs-sulfonimide, or C4Fg-sulfonimide anions; b) a butyl tail and sulfonate or CFs-sulfonimide anions; c) a MEE tail and sulfonate or CFs-sulfonimide anions. Data are represented as mean ± SD, N = 3. ns not synthesized.

[0089] FIGS. 11A-11 E show the apparent viscosity of zwitterionic liquids, a) Log-log plot of apparent viscosity as a function of shear rate; b-d) semi-log plot of apparent viscosity at a shear rate of 1 s-1as a function of b) spacer length, c) Tg, and d) molar heat capacity change at Tgfor e) supercooled zwitterions: 3 and 10 and zwitterionic liquids (ZILs): 13-15, 17, and 18. Dashed lines and open data points denote supercooled liquids; solid lines and filled points denote ZILs. Data are shown as mean ± SD, n = 3.

[0090] FIGS. 12A-12C show the dielectric properties of neat zwitterions, (a) Relative storage permittivity er(series circuit model) as a function of dielectric frequency ffor supercooled zwitterions: 3 and 10 and ZILs: 13-15, 17, and 18; timescales (i) and (ii) correspond to dipole bias and electrode charging, respectively, (b) Dielectric loss tangent, tan(d), for these zwitterions as a function of dielectric frequency, (c) Static dielectric constant of ersof these zwitterions as a function of spacer length; data points mean ± SD of plateau region for each molecule. Dashed lines and open data points denote supercooled liquids; solid lines and filled points denote stable liquids.

[0091] FIG. 13 shows examples of zwitterionic liquids including macro-zwitterionic liquids (Macro-ZILs), wherein the charges of the zwitterion are displaced by a long polymer, main-chain polyampholytes (PAs), wherein a plurality of charges are distributed throughout the main-chain, polyzwitterionic liquids (Poly(ZIL)s), wherein a plurality of zwitterions are attached as pendant groups to a polymer backbone, and pendant PAs, wherein singly charged subunits are attached as pendant groups to a polymer backbone.

[0092] FIG. 14 shows examples of synthetic pathways to macroZILs, main-chain polyampholytes, pendent polyampholytes, and poly(ZIL)s.

[0093] FIG. 15 shows examples of synthetic pathways to block copolymers.

[0094] FIG. 16 shows examples of synthetic pathways from terminal polarmer dithiols to diacrylates and dibenzophenones for thermal and photocrosslinking.

[0095] DETAILED DESCRIPTION

[0096] Provided herein are compounds and polymers (FIGS. 1A-1 B, FIG. 13). Soft electronic and robotic devices are driving demand for compliant materials with exceptional functional properties. While a broad palette of soft conductors exists, soft dielectrics that exhibit both high permittivity and mechanical compliance are lacking. Here, we report the rational design and synthesis of zwitterions composed of cation-anion pairs bound by a covalent tether. Most zwitterions possess high melting (Tm) and glass (Tg) transition temperatures, which limit their use under ambient conditions. Remarkably, ZILs of the invention, e.g., containing a 16-atom inter-charge spacer, flexible tail on the imidazolium cation, and a CFs-sulfonimide anion, exhibited more than a 100-fold reduction in 77 at room temperature compared to their supercooled counterparts with shorter spacers. Moreover, their static dielectric permittivity, ^s, increased from -240 to -420 with increasing inter-charge spacer length (from 4 to 16 atoms), which represents the highest values reported to date for soft materials.

[0097] Compounds and polymers described herein are advantageous as their polarizability and mechanical response enable application in elements such as dielectric actuators, capacitors, field effect transistors, and batteries. Compounds described herein may also be liquids at room temperature.

[0098] Compounds

[0099] The compounds have a general formula Ry-Y-Rb-X-Rx. X is a negatively charged functional group, Y is a positively charged functional group, Rb is a linker, e.g., of at least 3 atoms long, Ry is C>1 hydrocarbyl or C>1 heterohydrocarbyl, and Rx is absent, C>1 hydrocarbyl, or C>1 heterohydrocarbyl.

[0100] Exemplary anionic groups, X, include:

[0101] Exemplary cationic groups, Y, include heterocycles, e.g., nitrogen-containing heterocycles such as a five- or six-membered heterocycles. Examples of Y include 1 ,2,3-triazoliums, 1 ,2,4-triazoliums, pyridiniums, tetrazoliums, and imidazoliums, e.g., imidazolium and 2-methyl imidazolium. Other cationic groups include ammonium, phosphonium, and sulfonium groups, as described herein, e.g., wherein a hydrocarbyl or heterohydrocarbyl group is replaced with a hydrocarbylene or heterohydrocarbylene group.

[0102] The linker may be any suitable group including hydrocarbylene or heterohydrocarbylene. For example, linkers include alkylene groups or ether, polyether, thioether, or polythioether groups. The length of the linker can be between 3-30 atoms, e.g., 3-6 atoms, 4-20 atoms, 5-20 atoms, 9-12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms. Examples of Rb include propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene, heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene, hexacosylene, heptacosylene, octacosylene, nonacosylene, or triacontylene and heterohydrocarbyl equivalents thereof, e.g., with 1 to 10 O or S atoms replacing a C atom in the main chain. A linker may also include a polyalkylene glycol (thiol) portion (e.g., 2 to 5 repeating units) and an alkylene portion (e.g., 2 to 10 atoms in the main chain). In some embodiments, Rb is a linker of at least 5 atoms long, or Rb is C>1 heterohydrocarbylene. In some embodiments, the linker is polymeric, e.g., including polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane. The linker may be a polymer with a molecular weight between 100 g / mol and 1 ,000,000 g / mol (e.g., about 100 g / mol, 200 g / mol, 500 g / mol, 1 ,000 g / mol, 2,000 g / mol, 5,000 g / mol, 10,000 g / mol, 20,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 500,000 g / mol, or 1 ,000,000 g / mol, between 100 g / mol and 1 ,000 g / mol, between 1 ,000 g / mol and 10,000 g / mol, between 10,000 g / mol and 100,000 g / mol, between 100,000 g / mol and 1 ,000,000 g / mol, between 100 g / mol and 10,000 g / mol, between 1 ,000 g / mol and 100,000 g / mol, between 10,000 g / mol and 1 ,000,000 g / mol, between 100 g / mol and 100,000 g / mol, 1 ,000 g / mol and 1 ,000,000 g / mol, and between 100 g / mol and 1 ,000,000 g / mol. In some embodiments, the number of repeating units in a polymeric linker is 10-25,000, e.g., 100-1000, 1000-5000, 5000-10,000, or 10,000- 20,000. Preferably, the polymeric linker is charge neutral. The Tgof the linker is preferably below 25 °C.

[0103] Rx is absent for groups such as sulfonate, carboxylate, and trifluoroboronate. For other anionic groups, Rx may be C>1 hydrocarbyl or C>1 heterohydrocarbyl. Rx may be substituted by a polymerizable group, such as alkenyl or alkynyl group. The Rx group can have a main chain of 1-30 atoms, e.g., 1 to 10 atoms, 3-10 atoms, 6-9 atoms, 9-12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms. Exemplary Rx groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl (e.g., perfluorinated). Rx may include a terminal reactive group. Exemplary terminal reactive groups include an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone.

[0104] RY may be C>3 hydrocarbyl or C>3 heterohydrocarbyl. RY may be substituted by a terminal reactive group. Exemplary terminal reactive groups include an acrylate, an acrylic acid, an ester (e.g., N- hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone. The RY group can have a main chain of between 1-30 atoms, e.g., 1-10 atoms, 3-10 atoms, 6-9 atoms, 9- 12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms. In some embodiments, RY is C>5 heterohydrocarbyl.

[0105] Examples of compounds are shown in Table 1 :

[0106] independently an integer between 1 and 1000.

[0107] Polymers

[0108] The disclosure provides various zwitterionic polymers (FIGS. 13-16). In one embodiment, the polymer has a backbone that includes charged subunits. The charged subunits may be of the formula -RA-Z-RB-. The subunits can be polymerized via a terminal reactive group in the precursor to RA or RB or attached onto an existing polymer chain via a linking moiety. The backbone may include polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polyalkylene (e.g., polyethylene or polypropylene), polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyurethane, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or a combination thereof. The terminal reactive group or linking moiety may include an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone. In the subunit, Z may be a negatively or positively charged functional group, wherein the negatively charged functional group may include . Exemplary positively charged groups include heterocycles, e.g., nitrogen-containing heterocycles such as a five- or six-membered heterocycles. Examples of Z include 1 ,2,3-triazoliums, 1 ,2,4-triazoliums, pyridiniums, tetrazoliums, and imidazoliums.

[0109] In the subunit, RA is a C>1 hydrocarbylene, C>1 heterohydrocarbylene, or C>1 heterohydrocarbylene. RA may be substituted by a terminal reactive group prior to polymerization. Exemplary terminal reactive groups include an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone. The RA group can have a main chain of between 1-30 atoms, e.g., 1-10 atoms, 3-10 atoms, 6-9 atoms, 9-12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms.

[0110] In the subunit, RB is a C>1 hydrocarbylene, C>1 heterohydrocarbylene, or C>1 heterohydrocarbylene. RB may be substituted by a terminal reactive group prior to polymerization. Exemplary terminal reactive groups include an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone. The RB group can have a main chain of between 1-30 atoms, e.g., 1-10 atoms, 3-10 atoms, 6-9 atoms, 9-12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms.

[0111] Exemplary subunits may include any of the subunits of the following table:

[0112] , wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000. Additional examples of polymers may be any of the polymers of the following table:

[0113] , wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000. The positive and negative charges can alternate, be randomly distributed, or in blocks, based on the reactive groups and polymerization chemistry employe, which is within the skill of one in the art.

[0114] It will be understood that perfect charge neutrality in a given polymer may not be present. In some embodiments, the negatively and positively charged functional groups are present in the polymer in a ratio between 4:5 and 5:4, e.g., for every four negatively charged functional groups, 5 positively charged functional groups are present to form a ratio of 4:5, or for every five negatively charged functional groups, 4 positively charged functional groups are present to form a ratio of 5:4. Exemplary ratios of positively and negatively charged functional groups include a ratio between 4:5 and 5:4, including 4:5, 5:6, 6:7. 7:8, 8:9, 9:10, 24:25, 49:50, 99:100, 999:1000, 1 :1 , 1000:999, 100:99, 50:49, 25:24, 10:9, 9:8, 8:7. 7:6, 6:5, and 5:4.

[0115] The disclosure also provides polymers having a backbone and including two or more singly charged pendant groups or at least one zwitterionic pendant group. For example, the pendant group may be of the singly charged form -RA-Z-RB, wherein each Z may be independently a negatively or positively charged functional group, each RA is independently a C>1 hydrocarbylene or C>1 heterohydrocarbylene, and each RB is independently absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl. In another example, the pendant group may of the zwitterionic form -Ry-Y-Rb-X-Rx or -Ry-X-Rb-Y-Rx, wherein each X is independently a negatively charged functional group, each Y is independently a positively charged functional group, each Rb is independently a linker, e.g., of at least 3 atoms long, Ry is a C>1 hydrocarbylene or a C>1 heterohydrocarbylene, and Rx is absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl. The compounds can be polymerized via a terminal reactive group attached to RA, RB, Rx, or Ry, or attached onto an existing polymer chain via a linking moiety, e.g., a thiol. That is a monomer for the backbone may be functionalized with the charged groups before or after polymerization. The backbone or Rb may include polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polyalkylene (e.g., polyethylene or polypropylene), polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyurethane or a combination thereof. The terminal reactive group may include an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone. Pendant groups can be attached to the polymer chain through any known conjugation chemistry including click chemistry, condensation reactions, thiol-ene, etc. Suitable linking moieties will be present, e.g., alkene, thiol, azide, alkyne, an acrylate, an acrylic acid, an ester (e.g., N-hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone, electrophilic centers such as haloalkane, or nucleophilic groups including thiol, hydroxyl, or amine for the conjugation. Polymers may also have other pendant groups, e.g., heterohydrocarbyl, e.g., polyethylene glycol, hydrocarbyl, aryl, heteroaryl, cycloalkyl, polysiloxane, polyacrylate, poly methacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane.

[0116] The linker, Rb, may be any suitable group including hydrocarbylene or heterohydrocarbylene. For example, linkers include alkylene groups or ether, polyether, thioether, or polythioether groups. The length of the linker can be between 3-30 atoms, e.g., 3-6 atoms, 4-20 atoms, 5-20 atoms, 9-12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms. Examples of Rb include propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, icosylene, heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene, hexacosylene, heptacosylene, octacosylene, nonacosylene, or triacontylene and heterohydrocarbyl equivalents thereof, e.g., with 1 to 10 O or S atoms replacing a C atom in the main chain. A linker may also include a polyalkylene glycol (thiol) portion (e.g., 2 to 5 repeating units) and an alkylene portion (e.g., 2 to 10 atoms in the main chain). In some embodiments, Rb is a linker of at least 5 atoms long, or Rb is C>1 heterohydrocarbylene. In some embodiments, the linker includes polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane. The linker may be a polymer with a molecular weight between 100 g / mol and 1 ,000,000 g / mol (e.g., about 100 g / mol, 200 g / mol, 500 g / mol, 1 ,000 g / mol, 2,000 g / mol, 5,000 g / mol, 10,000 g / mol, 20,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 500,000 g / mol, or 1 ,000,000 g / mol, between 100 g / mol and 1 ,000 g / mol, between 1 ,000 g / mol and 10,000 g / mol, between 10,000 g / mol and 100,000 g / mol, between 100,000 g / mol and 1 ,000,000 g / mol, between 100 g / mol and 10,000 g / mol, between 1 ,000 g / mol and 100,000 g / mol, between 10,000 g / mol and 1 ,000,000 g / mol, between 100 g / mol and 100,000 g / mol, 1 ,000 g / mol and 1 ,000,000 g / mol, and between 100 g / mol and 1 ,000,000 g / mol. In some embodiments, the number of repeating units in a polymeric linker is 10-25,000, e.g., 100-1000, 1000-5000, 5000-10,000, or 10,000- 20,000. Preferably, the polymeric linker is charge neutral. The Tgof the linker is preferably below 25 °C.

[0117] RB and Rx are absent for negatively charged functional groups such as sulfonate, carboxylate, and trifluoroboronate. For other anionic groups, each RB and Rx may be independently a C>1 hydrocarbyl or a C>1 heterohydrocarbyl. Each RB and Rx group can have independently a main chain of 1-30 atoms, e.g., 1 to 10 atoms, 3-10 atoms, 6-9 atoms, 9-12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms. Exemplary RB and Rx groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl (e.g., perfluorinated). Each RB and Rx may include independently a terminal reactive group. Exemplary terminal reactive groups include an acrylate, an acrylic acid, an ester (e.g., N- hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone.

[0118] Each RA and RY is independently a C>1 hydrocarbylene, C>1 heterohydrocarbylene, or C>1 heterohydrocarbylene. Each RA and RY may be independently substituted by a terminal reactive group prior to attachment of the pendant group to the backbone or polymerization of the pendant groups. Exemplary terminal reactive groups include an acrylate, an acrylic acid, an ester (e.g., N- hydroxysuccinimide ester), an acetal, a disulfide, an alkene, e.g., n-butenyl, pentenyl, or hexenyl, an alkyne, e.g., a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, e.g., mesylate or tosylate, a hydrazine, a ketone, e.g., dibenzophenone, or a vinylsulfone. Each RA and RY group can have independently a main chain of between 1-30 atoms, e.g., 1-10 atoms, 3- 10 atoms, 6-9 atoms, 9-12 atoms, 12-15 atoms, 15-18 atoms, 18-21 atoms, 21-24 atoms, 24-27 atoms, or 27-30 atoms. In some embodiments, each RA and RY are independently a C>5 heterohydrocarbylene.

[0119] In a singly charged pendant group, each Z may be independently a negatively or positively charged functional group. In zwitterionic pendant groups, each X is independently a negatively charged functional group, and each Y is independently a positively charged functional group. The negatively charged functional group may include some embodiments, Z or X includes a negatively charged

[0120] N or B atom, e.g., . Exemplary positively charged groups include heterocycles, e.g., nitrogen-containing heterocycles such as a five- or six-membered heterocycles. Examples of Z or Y include 1 ,2,3-triazoliums, 1 ,2,4-triazoliums, pyridiniums, tetrazoliums, and imidazoliums. Other cationic groups include ammonium, phosphonium, and sulfonium groups, as described herein, e.g., wherein a hydrocarbyl or heterohydrocarbyl group is replaced with a hydrocarbylene or heterohydrocarbylene group.

[0121] For singly charged pendant groups, the positive and negative charges can alternate, be randomly distributed, or in blocks, based on the reactive groups and polymerization chemistry employe, which is within the skill of one in the art.

[0122] It will be understood that perfect charge neutrality in a given polymer may not be present. For singly charged pendant groups, the negatively and positively charged functional groups are present in the polymer in a ratio between 4:5 and 5:4, e.g., for every four negatively charged functional groups, 5 positively charged functional groups are present to form a ratio of 4:5, or for every five negatively charged functional groups, 4 positively charged functional groups are present to form a ratio of 5:4. Exemplary ratios of positively and negatively charged functional groups include a ratio between 4:5 and 5:4, including 4:5, 5:6, 6:7. 7:8, 8:9, 9:10, 24:25, 49:50, 99:100, 999:1000, 1 :1 , 1000:999, 100:99, 50:49, 25:24, 10:9, 9:8, 8:7. 7:6, 6:5, and 5:4.

[0123] Exemplary zwitterionic pendant groups include independently an integer between 1 and 1000. Exemplary polymers with zwitterionic pendants include , wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000. Exemplary singly charged pendant groups may be of the following table:

[0124] , wherein m is an integer between 0 and 19, wherein n, p and q are independently an integer between 1 and 1000, and wherein r is an integer between 0 and 10. The groups in this table may also be made divalent for inclusion in the main chain of any compound or polymer herein or within a pendant group of any polymer described herein. Exemplary polymers with singly charged pendants may be of the following table:

[0125]

[0126]

[0127]

[0128] Polymers with charged pendant groups may include a combination of singly charged and zwitterionic pendant groups.

[0129] When reacted with groups on a polymer, the stoichiometry may be controlled so that essentially all (>99%) linking moieties on the backbone are bound to a pendant group. Alternatively, less than all of the linking moieties may be reacted, e.g., between 25 and 75% may be unreacted. Unreacted linking moieties may be retained in the polymer or used for further reactions, e.g., with a second pendant group or crosslinker. Polymers may contain more than one pendant group of the invention. Polymers with more than one monomer may be random, alternating, or block copolymers. As described, polymers may be crosslinked with a crosslinking agent as is known in the art. Examples of polymers are: wherein n, a, b, and c are integers from 10-1000, and R is R is heterohydrocarbyl, e.g., polyethylene glycol, hydrocarbyl, aryl, heteroaryl, cycloalkyl, polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane.

[0130] Polymers of the invention may be terminated by various functional groups depending on the polymerization chemistry and as known in the art. Examples of terminating functional groups include Z or

[0131]

[0132] 0 and 20, and wherein R is a halo, hydrocarbyl, heterohydrocarbyl, carbocyclyl, heterocyclyl, aryl, or heteroaryl group. Terminal groups may also allow for crosslinking, e.g., thermally or photochemically (FIG. 16).

[0133] The disclosure provides block copolymers including any of the polymers described above, including the polymers with charged subunits in the main chain, the polymers with singly charged pendant groups, and the polymers with zwitterionic pendant groups. Block copolymers with charged polymers and neutral polymers are also encompassed. The disclosure also provides cross-linked polymers including any of the polymers described above, including the polymers with charged subunits in the main chain, the polymers with singly charged pendant groups, and the polymers with zwitterionic pendant groups.

[0134] Uses

[0135] The compound and polymers of the disclosure may be used as dielectric materials, e.g., in a dielectric elastomer actuator, capacitor, hydraulically amplified self-healing electrostatic (HASEL) actuator, transistor, or battery. The compound or polymer can be placed between two separated electrodes that are connected to a power supply, and, once a voltage is applied through the power supply to the two electrodes, the compound or polymer can polarize in response to the electric field generated between the two electrodes, e.g., to produce strain or store energy. In another embodiment, the compound or polymer forms a gate dielectric in a field effect transistor. In another embodiment, the compound or polymer are a solid-state or gel-phase electrolyte in a battery containing an anode and a cathode to store electrical energy.

[0136] Examples

[0137] EXAMPLE 1 :

[0138] Materials. Dichloromethane (99.9 %) (Avantor Performance Material LLC), 1 -methylimidazole (99.0 %), 1 - ethylimidazole (98.0 %) (TCI America), toluene (anhydrous, 99.5 %), 2,2,2-trifluoroethanol (99%) (BeanTown Chemical), tetrahydrofuran (THF, 99%, stabilized ACS), hexane (98.5 %, mixture of isomers, ACS), acetonitrile (99.9%, anhydrous, Hi PerSolv CHROMANORM® super gradient grade for HPLC), acetone (99.5 %), diethyl ether (Et20, 98%, stabilized), ethyl acetate (EtOAc, 99.5% ACS), glacial acetic acid (AcOH, 99.7-100.5 % ACS), methanol (MeOH, 99.8 % ACS, used for workups) (VWR Chemicals BDH®), KOH (85%, Reagent Grade), sodium sulfite (anhydrous ACS) (VWR), HPLC-grade methanol (99.9%, used for mass spectrometry), 1 ,4-butanesultone (98%), 1 ,3-propanesultone (98%), 1- butylimidazole (98%), imidazole (99%, ReagentPlus®), 2-methylimidazole (99%), magnesium sulfate (MgSO4, anhydrous, ReagentPlus®, 99.5%), sodium sulfate (99.0 %, anhydrous, granular), potassium carbonate (K2CO3, anhydrous, free-flowing, Redi-Dri™, ACS reagent, 99%), silica gel (technical grade, pore size 60 A, 40-63 pm particle size), 1-bromobutane (99%, ReagentPlus®), thionyl chloride (99%, ReagentPlus®), N,N-dimethylformamide (DMF, 99.8%, Anhydrous), 1 ,4-butanediol (99% ReagentPlus®), potassium fe / Y-butoxide (f-BuOK, 1.0 M in THF), lithium bis(trimethylsilyl)amide solution (Li-HMDS, 1.0 M in THF), tetraethylene glycol (TetrEG, 99 %), butylated hydroxytoluene (BHT, 99 %) (Millipore Sigma), DMSO-cfe (99.9 % D, AcroSeal™), 6-chloro-1 -hexanol (97 %), Celite® 535 (Thermo Scientific Chemicals), high purity argon (AR HP300) (Airgas), 1-bromo-2-(2-methoxyethoxy)ethane (MEE-Br, 97 %) (Combi- Blocks), 1 -allylimidazole (97%), activated charcoal (DARCO® 4-12 mesh) (Avantor), trifluoromethanesulfonamide (triflamide, 98%), and perfluorobutanesulfonyl fluoride (95%) (Oakwood Chemical) were used as received without further purification unless otherwise noted.

[0139] Instrumentation.1H NMR (400.2 MHz),13C NMR (100.6 MHz), and19F NMR (376.5 MHz) were collected using a 400 MHz Bruker AVANCE NEO NMR spectrometer equipped with a 5 mm RT double resonance broad banded iProbe. Products were dissolved (20 pM) in HPLC-grade MeOH and measured via positive ion (zwitterions, L, N) and negative ion (sulfonate, sulfonimide, and C4Fg-sulfonamide intermediates) electrospray ionization on a Bruker Impact II q-TOF mass spectrometer equipped with an Agilent 1260 HPLC system using flow injection analysis. The samples were introduced into the mass spectrometer using 60% acetonitrile with 0.1 % formic acid through the HPLC system. The mass scale was internally calibrated using sodium formate clusters which were introduced at the end of each run to achieve high mass accuracy. Differential scanning calorimetry (DSC) was conducted on a TA instruments Discovery 250 calorimeter. All zwitterions were dried for 24 h at 115 °C in a vacuum oven, stored under high purity argon, and quickly transferred to aluminum pans and hermetically sealed for characterization. Roomtemperature solids were subjected to heat-cool-heat cycles, and liquids to cool-heat cycles (all ramp rates 10 °C min-1, with equilibration and 5 minute isotherms at each maximum and minimum) followed by a ramp to 25 °C at 20 °C min1. Tgwas determined by taking the mean from the cooling and subsequent heating cycles. ACgwas determined as the difference between extrapolated liquid and glass heat capacities at Tgduring heating. Rheology was conducted on a TA Instruments Discovery Hybrid HR20 rheometer with an 8 mm parallel plate geometry and a 400 pm gap. All liquids were dried for 24 h at 115 °C in a vacuum oven, then immediately transferred to the rheometer for measurement. Dielectric spectroscopy was conducted on a TA Instruments Discovery Hybrid HR20 rheometer with 25 mm custom dielectric parallel plate geometries equipped with a Keysight E4980A LCR meter and operating with 100 mV oscillation amplitude and a 100 pm gap. All molecules were dried for 24 h at 115 °C in a vacuum oven, then stored under high purity argon and transferred to the rheometer for measurement. Molecules 3 and 10 were placed on the bottom electrode as dry powders and heated to 150 °C for 5 minutes. Then, the top electrode was lowered into place and the apparatus quenched to 25 °C before measuring.

[0140] A note regarding safety with refluxing thionyl chloride. All reactions using refluxing thionyl chloride should be run and quenched with care as thionyl chloride reacts violently with water to produce concentrated acid and sulfur dioxide vapor. This vapor is caustic, toxic, and can damage infrastructure, including the downstream ductwork of a fume hood. To prevent large-scale release of concentrated acid and sulfur dioxide vapor during reaction and quenching, evolved gas should be routed through a vacuum trap to prevent back-suck, followed by a gas scrubber composed of a glass sparger and concentrated aqueous base; we used a stirring, 5 L bath of 5 M KOH. While quenching with ice pellets, it is important to maintain a high stirring rate because liquid water is immiscible with the crude product mixture. A low stirring rate enables formation of a reservoir of liquid water, which can lead to a violent runaway reaction. To avoid this, we maintain a high stirring rate and incremental addition of ice pellets while keeping the reaction vessel at 0 °C. This note applies to the synthesis of sulfonyl chloride intermediates A, D, G, and J.

[0141] Synthesis of 1. 4.411 g (40.8 mmoles) 1 -allylimidazole was combined with 5.138 g (37.7 mmoles) 1 ,4- butanesultone and 41 mg (0.19 mmoles) in a 20 mL scintillation vial and heated to 80 °C with stirring for 43.5 hours, then stopped by removing from heat. The solid pellet of product was collected by breaking the vial, separating glass fragments, grinding the product in a mortar and pestle, washing with 3x40 mL of acetone, and drying under reduced pressure to afford 1 as a white powder in 7.531 g (82 %) yield.1H NMR (400.2 MHz, DMSO-c / 6, 8): 9.41-9.29 (s, 1 H), 7.92-7.85 (s, 1 H), 7.82-7.75 (s, 1 H), 6.15-5.98 (m, 1 H), 5.41-5.24 (m, 2H), 4.94-4.81 (d, 2H), 4.31-4.14 (t, 2H), 2.58-2.42 (t, 2H), 2.00-1.81 (m, 2H), 1.66-1.46 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.30 (s, 1 C), 131.85 (s, 1 C), 122.68 (s, 1 C), 122.50 (s, 1C), 120.23 (s, 1 C), 50.79 (s, 1 C), 50.55 (s, 1 C), 48.63 (s, 1 C), 28.64 (s, 1 C), 21.82 (s, 1 C). ESI (m / z): 245.0965 (CioHi7N203S+, calculated 245.0954).

[0142] Synthesis of 2. 118.2 g (952 mmoles) 1 -butylimidazole was combined with 121 .0 g (889 mmoles) 1 ,4- butanesultone in a 500 mL round-bottom flask, then heated to 80 °C with stirring for 24 h to afford a white, solid hemisphere in the bottom of the flask. The flask was broken, glass fragments removed, and the solids ground in a mortar and pestle under acetone, then isolated and washed with 3 x 500 mL acetone to afford 2 as a white powder in 230.95 (99.8 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 9.41-9.34 (s, 1 H), 7.90-7.83 (m, 2H), 4.28-4.14 (m, 4H), 2.55-2.45 (t, 2H), 1.97-1.84 (m, 2H), 1.84-1.72 (m, 2H), 1.64-1.49 (m, 2H), 1.34-1.17 (m, 2H), 0.97-0.83 (t, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.19 (s, 1 C), 122.52 (s, 1C), 122.43 (s, 1 C), 50.53 (s, 1 C), 48.54 (s, 1 C), 48.50 (s, 1 C), 31.31 (s, 1 C), 28.64 (s, 1 C), 21.81 (s, 1 C), 18.78 (s, 1 C), 13.26 (s, 1 C). ESI (m / z): 261.1268 (C11H21N2O3S+, calculated 261.1267). Synthesis of 3. 1 .254 g (7.37 mmoles) L was combined with 1 .010 g (7.42 mmoles) 1 ,4-butanesultone and 7 mL acetone in a 20 mL scintillation vial and heated to 50 °C with stirring for 120 hours, then returned to room temperature and precipitated in 12 mL Et2<D. The dense phase was 5x (diluted to 2 mL in MeOH and precipitated in 12 mL EtOAc) followed by 3x (dilute to 2 mL in MeOH and precipitate in 12 mL Et2<D). The viscous liquid was then sonicated in 15 mL Et2<D to induce crystallization, Et2<D was decanted, the solid pellet broken into a powder, and sonicated in 15 mL additional Et2<D before centrifuging, decanting, and leaving at reduced pressure for 24 h to remove residual Et2<D to afford 3 as a white powder in 1.26 g (56 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 9.26-9.19 (s, 1 H), 7.86-7.80 (m, 1 H), 7.80-7.74 (m, 1 H), 4.43-4.28 (m, 2H), 4.28-4.15 (m, 2H), 3.83-3.72 (m, 2H), 3.60-3.49 (m, 2H), 3.46-3.37 (m, 2H), 3.27-3.16 (s, 3H), 2.49-2.43 (m, 2H), 1.96-1.82 (m, 2H), 1.62-1.48 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.46 (s, 1 C), 122.75 (s, 1 C), 122.29 (s, 1 C), 71.07 (s, 1 C), 69.35 (s, 1 C), 68.08 (s, 1 C), 58.08 (s, 1 C), 50.46 (s, 1 C), 48.78 (s, 1 C), 48.58 (s, 1 C), 28.70 (s, 1 C), 21.78 (s, 1 C). ESI (m / z): 307.1337 (Ci2H23N2O5S+, calculated 307.1322).

[0143] Synthesis of 4. 1.019 g (3.36 mmoles) B-CF3 (as conjugate acid), 2.709 g (33.0 mmoles) 1- methylimidazole, 1.053 g (7.62 mmoles) K2CO3, and 415 mg (3.45 mmoles) MgSC were combined in a 20 mL scintillation vial and heated to 80 °C for 48 h, returned to room temperature, centrifuged to remove solids, then precipitated into acetone. Then, the resulting solids were 3x (diluted into 10 mL trifluoroethanol and precipitated into 150 mL Et2<D) afford 4 as a white, crystalline solid in 1 .07 g (91 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 9.15-9.09 (s, 1 H), 7.79-7.74 (m, 1 H), 7.73-7.68 (m, 1 H), 4.26- 4.15 (m, 2H), 3.90-3.80 (s, 3H), 3.06-2.98 (m, 2H), 1.98-1.85 (m, 2H), 1.71-1.58 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.61 (s, 1 C), 124.93-115.26 (q, 1 C), 123.68 (s, 1 C), 122.25 (s, 1 C), 53.60 (s, 1 C), 48.24 (s, 1 C), 35.75 (s, 1 C), 28.02 (s, 1C), 20.46 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.51 (s, 3F). ESI (m / z): 350.0454 (CgHisFsNsC^, calculated 350.0451).

[0144] Synthesis of 5. 1.031 g (3.39 mmoles) B-CF3 (as conjugate acid), 3.184 g (33.1 mmoles) 1- ethylimidazole, 1.017 g (7.36 mmoles) K2CO3, and 415 mg (3.45 mmoles) MgSC were combined in a 20 mL scintillation vial and heated to 80 °C for 48 h, returned to room temperature, centrifuged to remove solids, then precipitated into acetone. Then, the resulting solids were 3x (diluted into 10 mL trifluoroethanol and precipitated into 150 mL Et2<D) to afford 5 as a white, crystalline solid in 960 mg (78 %) yield1H NMR (400.2 MHz, DMSO-cfe, 8): 9.22-9.15 (s, 1 H), 7.84-7.75 (m, 2H), 4.27-4.12 (m, 4H), 3.09- 2.97 (m, 2H), 2.00-1 .85 (m, 2H), 1 .73-1 .58 (m, 2H), 1 .48-1 .37 (t, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 135.73 (s, 1 C), 124.93-115.26 (q, 1 C), 122.39 (s, 1 C), 122.21 (s, 1 C), 53.57 (s, 1 C), 48.30 (s, 1 C), 44.25 (s, 1C), 27.96 (s, 1 C), 20.49 (s, 1 C), 14.91 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.52 (s, 3F) ESI (m / z): 364.0610 (CioHi7F3N304S2+, calculated 364.0607)

[0145] Synthesis of 6. 1.082 g (3.56 mmoles) B-CF3 (as conjugate acid), 1.857 g (17.2 mmoles) 1 -allylimidazole, 969 mg (7.01 mmoles) K2CO3, and 414 mg (3.44 mmoles) MgSO4were combined in a 20 mL scintillation vial and heated to 80 °C for 24 h, then returned to 20 °C, diluted to 20 mL in acetone, and centrifuged to remove solids before precipitating into 100 mL of Et2O. The resulting viscous brown oil was 2x (dissolved to 20 mL in acetone and precipitated in 100 mL of Et2O) and placed under low vac to afford 6 as a tan, crystalline solid (1.1 g, 82 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.25-9.11 (s, 1 H), 7.89-7.68 (m, 2H), 6.15-5.95 (m, 1 H), 5.45-5.23 (m, 2H), 4.92-4.77 (m, 2H), 4.33-4.14 (t, 2H), 3.08-2.98 (t, 2H), 2.03-1.85 (m, 2H), 1.74-1.58 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.15 (s, 1 C), 131.61 (s, 1 C), 124.94- 115.26 (q, 1 C), 122.62 (s, 1 C), 122.59 (s, 1 C), 120.32 (s, 1 C), 53.60 (s, 1 C), 50.94 (s, 1 C), 48.41 (s, 1 C), 28.00 (s, 1 C), 20.49 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.53 (s, 3F). ESI (m / z): 376.0614 (CnHi7F3N3O4S2+, calculated 376.0607).

[0146] Synthesis of 7. 5.007 g (10.2 mmoles) B-C4F9 was combined with 1 .107 g (10.2 mmoles) allylimidazole, 26 mg (0.12 mmoles) BHT, and 2 mL acetonitrile in a 20 mL scintillation vial, then heated to 80 °C with stirring for 24 h. Solids were removed by centrifugation, then the supernatant was combined with an equal volume of reverse osmosis water to induce crystallization and solvent was removed via air stream at 50 °C to afford a yellow solid. This was washed 2x with reverse osmosis water and the resulting solid dried via vacuum oven to afford 7 as a white, crystalline solid (3.54 g, 77%).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.22-9.15 (s, 1 H), 7.86-7.77 (m, 1 H), 7.77-7.70 (m, 1 H), 6.16-5.94 (m, 1 H), 5.45-5.21 (m, 2H), 4.94- 4.76 (m, 2H), 4.35-4.13 (t, 2H), 3.10-2.99 (t, 2H), 2.07-1.83 (m, 2H), 1.79-1.57 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.19 (s, 1 C), 131.62 (s, 1 C), 122.62 (s, 1 C), 122.59 (s, 1 C), 121.34-108.25 (br m, 4C, fluorinated), 120.26 (s, 1 C), 53.86 (s, 1 C), 50.95 (s, 1 C), 48.41 (s, 1 C), 28.00 (s, 1 C), 20.48 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8) -80.52 (m, 3F), -112.88 (m, 2F), -121.02 (m, 2F), -125.74 (m, 2F). ESI (m / z): 526.0491 (Ci4Hi7F9N3O4S2+, calculated 526.0511). Synthesis of 8. 1.044 g (3.44 mmoles) B-CF3 (as conjugate acid), 2.131 g (17.2 mmoles) 1- butylimidazole, 963 mg (6.97 mmoles) K2CO3, and 412 mg (3.42 mmoles) MgSO4 were combined in a 20 mL scintillation vial and heated to 80 °C for 24 h, then returned to 20 °C, diluted to 20 mL in acetone, and centrifuged to remove solids before precipitating into 100 mL of Et2O. The resulting viscous brown oil was 2x (dissolved to 20 mL in acetone and precipitated in 100 mL of Et2O) and placed under low vac to afford 8 as a tan, crystalline solid (1.1 g, 82 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.27-9.11 (s, 1 H), 7.87-7.72 (m, 2H), 4.33-4.05 (m, 4H), 3.08-2.98 (t, 2H), 2.00-1 .87 (m, 2H), 1 .84-1 .72 (m, 2H), 1 .72-1 .59 (m, 2H), 1.33-1.19 (m, 2H), 0.95-0.84 (t, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.00 (s, 1 C), 124.94-115.27 (q, 1 C), 122.52 (s, 1 C), 122.43 (s, 1 C), 53.60 (s, 1C), 48.65 (s, 1 C), 48.35 (s, 1 C), 31.25 (s, 1 C), 27.97 (s, 1 C), 20.48 (s, 1 C), 18.80 (s, 1 C), 13.20 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.60 (s, 3F). ESI (m / z): 392.0924 (Ci2H2iF3N3O4S2+, calculated 392.0920).

[0147] Synthesis of 9. 1.007 g (3.32 mmoles) B-CF3 (as conjugate acid), 2.301 g (16.6 mmoles) N, 927 mg (6.71 mmoles) K2CO3, and 398 mg (3.31 mmoles) MgSO4 were combined in a 20 mL scintillation vial and heated to 80 °C for 48 h, then returned to 20 °C, diluted to 15 mL in acetone, and centrifuged to remove solids before precipitating into 120 mL of Et2O. The resulting tan solid was washed with 3x 40 mL Et2O before placing under low vac to afford 9 as a tan powder in 716 mg (53 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 7.74-7.64 (m, 2H), 4.23-4.01 (m, 4H), 3.08-2.97 (t, 2H), 2.70-2.56 (s, 3H), 1.96-1.79 (m, 2H), 1.79-1.62 (m, 4H), 1.39-1.20 (m, 2H), 1.01-0.83 (t, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 143.76 (s, 1C), 124.94-115.27 (q, 1 C), 121.28 (s, 2C), 53.68 (s, 1 C), 47.31 (s, 1 C), 46.99 (s, 1 C), 31.03 (s, 1 C), 27.54 (s, 1 C), 20.55 (s, 1 C), 18.92 (s, 1C), 13.37 (s, 1 C), 9.09 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -7.51 (s, 3F). ESI (m / z): 406.1081 (Ci3H23F3N3O4S2+, calculated 406.1077).

[0148] Synthesis of 10. 5.009 g (14.7 mmoles) B-CF3 was combined with 17.494 g (103 mmoles) L, and 410 mg (2.97 mmoles) K2CO3, and 884 mg (7.34 mmoles) MgSO4 under an argon atmosphere, sealed, and heated to 80 °C for 48 hours. The mixture was returned to 20 °C, centrifuged (5 minutes, 4500 RPM) to remove solids, then the solids were washed with 3x10 mL acetone. The crude product and acetone washes were combined and left under reduced pressure for 24 h to remove acetone. Then, the crude product mixture was washed with 10 x 20 mL Et2O and purified by flash column chromatography (silica gel stationary phase, gradient eluent EtOAc 2:1 EtOAc:acetone) and concentrated under reduced pressure to afford 10 as an amber crystalline solid in 4.895 g (76 %) yield.1H NMR (400.2 MHz, DMSO- d6, 8): 9.15-9.10 (s, 1 H), 7.81-7.72 (m, 2H), 4.39-4.31 (t, 2H), 4.28-4.19 (t, 2H), 3.81 -3.73 (m, 2H), 3.59- 3.50 (m, 2H), 3.45-3.38 (m, 2H), 3.26-3.18 (s, 3H), 3.09-2.99 (t, 2H), 2.00-1.87 (m, 2H), 1.73-1.61 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.42 (s, 1 C), 124.97-115.30 (q, 1 C), 122.86 (s, 1 C), 122.20 (s, 1C), 71.09 (s, 1 C), 69.41 (s, 1 C), 68.06 (s, 1 C), 58.05 (s, 1 C), 53.63 (s, 1 C), 48.91 (s, 1 C), 48.35 (s, 1 C), 28.11 (s, 1 C), 20.49 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.57 (s, 3F). ESI (m / z): 438.0978 (CI3H23F3N3O6S2+, calculated 438.0975).

[0149] Synthesis of 11. 349 mg (1.15 mmoles) B-CF3 (as conjugate acid) was combined with 1.02 g (5.54 mmoles) O, 319 mg (2.31 mmoles) K2CO3, and 141 mg (1 .17 mmoles) MgSO4 in a 20 mL scintillation vial and heated to 80 °C for 48 h with stirring before returning to room temperature, removing solids by centrifugation, and washing the resulting brown oil with 3 x 12 mL Et2O to afford 11 as a tan solid (392 mg, 76 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 7.77-7.57 (m, 2H), 4.38-4.24 (t, 2H), 4.24-4.10 (t, 2H), 3.79-3.67 (m, 2H), 3.56-3.46 (m, 2H), 3.44-3.35 (m, 2H), 3.25-3.16 (s, 3H), 3.09-2.97 (m, 2H), 2.69-2.58 (s, 3H), 1 .93-1 .78 (m, 2H), 1 .77-1 .63 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 144.53 (s, 1 C), 124.96-115.28 (q, 1 C), 121.61 (s, 1C), 121.19 (s, 1 C), 71.12 (s, 1 C), 69.55 (s, 1 C), 68.42 (s, 1 C), 58.05 (s, 1C), 53.69 (s, 1 C), 47.62 (s, 1 C), 47.03 (s, 1 C), 27.67 (s, 1 C), 20.55 (s, 1 C), 9.33 (s, 1 C).19F NMR (376.5 MHz, DMSO-C / 6, 8): -77.50 (s, 3F). ESI (m / z): 452.1140 (CI4H25F3N3O6S2+, calculated 452.1131).

[0150] Synthesis of 12. 613 mg (1 .66 mmoles) E was combined with 1 .23 g (9.91 mmoles) 1 -butylimidazole, 246 mg (1 .78 mmoles) K2CO3, and 126 mg (1 .04 mmoles) MgSO4, in a 20 mL scintillation vial, then heated to 80 °C with stirring for 48 h. Solids were removed by centrifugation, then the product was washed with 5 x 12 mL Et2O to afford 12 as a tan powder (625 mg, 90 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.23-9.13 (s, 1 H), 7.85-7.73 (m, 2H), 4.23-4.09 (m, 4H), 3.01-2.89 (t, 2H), 1.87-1.72 (m, 4H), 1.72-1.60 (m, 2H), 1.45-1.32 (m, 2 H), 1.32-1.18 (m, 4H), 0.96-0.85 (t, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 135.93 (s, 1 C), 124.97-115.30 (q, 1 C), 122.47 (s, 1 C), 122.44 (s, 1 C), 54.25 (s, 1 C), 48.75 (s, 1 C), 48.60 (s, 1 C), 31.23 (s, 1 C), 29.01 (s, 1 C), 26.88 (s, 1C), 25.03 (s, 1 C), 23.44 (s, 1 C), 18.78 (s, 1 C), 13.21 (s, 1 C).19F NMR (376.5 MHz, DMSO-c / 6, 8): -77.52 (s, 3F). ESI (m / z): 420.1238 (CI4H25F3N3O4S2+, calculated 420.1233).

[0151] Synthesis of 13. 1 .02 g (2.76 mmoles) E, 2.98 g (17.5 mmoles) L, 387 mg (2.80 mmoles) K2CO3, and 178 mg (1 .48 mmoles) MgSO4 were combined in a 20 mL scintillation vial and stirred at 80 °C for 50 h. The crude reaction mixture was cooled to 20 °C, then washed with 3 x 12 mL Et2O and purified by flash column chromatography (29.8 g silica, acetone eluent) to afford 13 as a viscous brown oil (817 mg, 64 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.21-9.05 (s, 1 H), 7.87-7.67 (m, 2H), 4.41 -4.29 (t, 2H), 4.25-4.13 (t, 2H), 3.85-3.71 (m, 2H), 3.61 -3.49 (m, 2H), 3.47-3.36 (m, 2H), 3.24-3.18 (s, 3H), 3.01-2.91 (t, 2H), 1 .88- 1 .73 (m, 2H), 1 .73-1 .61 (m, 2H), 1 .47-1 .32 (m, 2H), 1 .32-1 .17 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.35 (s, 1 C), 124.99-115.32 (q, 1 C), 122.78 (s, 1 C), 122.20 (s, 1 C), 71.08 (s, 1 C), 69.37 (s, 1 C), 68.04 (s, 1 C), 58.06 (s, 1 C), 54.30 (s, 1C), 48.86 (s, 1 C), 48.76 (s, 1 C), 29.14 (s, 1 C), 26.95 (s, 1 C), 25.05 (s, 1 C), 23.47 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.55 (s, 3F). ESI (m / z): 488.1115 (Ci5H27F3N3O6S2+, calculated 488.1107).

[0152] Synthesis of 14. 5.67 g (14.2 mmoles) H was combined with 17.13 g (138 mmoles) 1 -butylimidazole, 2.29 g, (16.6 mmoles) K2CO3, and 2.13 g (17.7 mmoles) MgSC and heated to 80 °C with stirring for 48 h, then returned to room temperature and washed with 3x40 mL hexanes before purifying by flash column chromatography (135 g silica, mixed eluent starting with EtOAc, then switching to a gradient 1 :1 acetone:hexanes pure acetone) and concentrated under reduced pressure to afford 14 as a viscous brown oil in 5.79 g (91 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 9.24-9.07 (s, 1 H), 7.88-7.69 (m, 2H), 4.29-4.08 (m, 4H), 3.53-3.28 (m, 4H), 3.13-2.92 (t, 2H), 2.02-1.68 (m, 6H), 1.61 -1.39 (m, 2H), 1.38-1.15 (m, 2H), 1.01-0.80 (t, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 135.90 (s, 1 C), 124.96-115.29 (q, 1 C), 122.44 (s, 1 C), 122.42 (s, 1 C), 69.07 (s, 1 C), 68.12 (s, 1 C), 51.79 (s, 1 C), 48.76 (s, 1 C), 48.63 (s, 1 C), 31.27 (s, 1 C), 26.57 (s, 1 C), 25.75 (s, 1C), 24.26 (s, 1 C), 18.78 (s, 1 C), 13.17 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.65 (s, 3F). ESI (m / z): 472.1174 (CI5H27F3N3O5S2+, calculated 472.1158).

[0153] Synthesis of 15. 1 g (2.5 mmoles) H was combined with 3.02 g (17.7 mmoles) L, 361 mg (2.6 mmoles) K2CO3, and 162 mg (1 .3 mmoles) MgSC and heated to 80 °C for 48 h, returned to room temperature, and washed with 3x40 mL Et2O and concentrated under reduced pressure to afford 15 as a viscous brown oil in 1.27 g (100 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 9.15-9.07 (s, 1 H), 7.82-7.70 (m, 2H), 4.40-4.29 (t, 2H), 4.27-4.17 (t, 2H), 3.83-3.72 (m, 2H), 3.59-3.50 (m, 2H), 3.49-3.35 (m, 6H), 3.24- 3.19 (s, 3H), 3.06-2.99 (t, 2H), 1 .96-1 .79 (m, 4H), 1 .55-1 .42 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.36 (s, 1 C), 124.98-115.30 (q, 1 C), 122.78 (s, 1 C), 122.19 (s, 1 C), 71.08 (s, 1 C), 69.37 (s, 1 C), 69.07 (s, 1C), 68.16 (s, 1 C), 68.03 (s, 1 C), 58.04 (s, 1 C), 51.79 (s, 1 C), 48.85 (s, 1 C), 48.74 (s, 1 C), 26.62 (s, 1 C), 25.74 (s, 1 C), 24.27 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.59 (s, 3F). ESI (m / z): 518.1238 (Ci6H29F3N3O?S2+, calculated 518.1213).

[0154] Synthesis of 16. 7.089 g (13.7 mmol) of K was combined with 1 .487 g (13.8 mmol) of 1 -allylimidazole and a stir bar under an argon atmosphere in a 20 mL scintillation vial, then stirred at 80 °C for 72 h. The reaction was stopped by removing from heat, then ran 3x (diluted to 12.5 mL in acetone, precipitated into 35 mL of Et2<D, shaken vigorously, centrifuged 4500 RPM for 120 s, decanted the buoyant phase). The product was purified by silica gel column chromatography using a gradient eluent (EtOAc 3:1 EtOAc:acetone), concentrated under reduced pressure, dried over MgSO4, then transferred to a vacuum oven for 24 h at 115 °C to afford 16 as an amber oil (5.6 g, 74 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.15-9.05 (s, 1 H), 7.81-7.74 (s, 1 H), 7.74-7.66 (s, 1 H), 6.13-5.98 (m, 1 H), 5.41-5.33 (dd, 1 H), 5.33-5.24 (dd, 1 H), 4.92-4.82 (d, 2H), 4.43-4.32 (t, 2H), 3.85, 3.75 (t, 2H), 3.62-3.43 (br m, 12 H), 3.43-3.34 (t, 2H), 3.04-2.93 (t, 2H), 1 .77-1 .65, (m, 2H), 1 .62-1 .51 , (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.44 (s, 1 C), 131 .69 (s, 2C overlapping), 125.01 -115.33 (q, 1 C, CF3), 123.02 (s, 1 C), 122.25 (s, 1 C), 120.12 (s, 1 C), 69.82 (s, 2C overlapping), 69.79 (s, 1 C), 69.72 (s, 1 C), 69.61 (s, 1 C), 69.56 (s, 1 C), 69.51 (s, 1 C), 68.06 (s, 1 C), 54.39 (s, 1 C), 50.87 (s, 1 C), 48.93 (s, 1 C), 27.87 (s, 1 C), 20.81 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.59 (s, 3F). ESI (m / z): 552.1666 (Ci9H33F3N3O8S2+, calculated 552.1656).

[0155] Synthesis of 17. K (334 mg, 0.645 mmoles) was combined with 1 -butylimidazole (1.22 g, 9.83 mmoles) K2CO3 (111 mg, 0.803 mmoles), and MgSC (22 mg, 0.183 mmoles) under argon in a 20 mL scintillation vial. The mixture was sealed and heated to 80 °C with stirring for 48 h. Solids were removed by centrifugation and washed with acetone. Then, the crude liquid phase and acetone washes were combined, solvent was removed in vacuo, then the mixture washed with 3x10 mL hexanes. Then, the crude product was purified by flash column chromatography (10 g silica, gradient eluent EtOAc acetone) and concentrated under vacuum to afford 380 mg 17 (100 %) as an amber oil.1H NMR (400.2 MHz, DMSO-cfe, 8): 9.15-9.08 (s, 1 H), 7.82-7.72 (s+s, 2H overlapping), 4.40-4.29 (t, 2H), 4.25-4.14 (t, 2H), 3.84-3.73 (t, 2H), 3.62-3.43 (br m, 12H), 3.43-3.34 (t, 2H), 3.01 -2.94 (t, 2H), 1.84-1.64 (br m, 4H), 1.63-1.50 (m, 2H), 1.33-1.19 (m, 2H), 0.96-0.84 (t, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.30 (s, 1 C), 124.99-115.31 (q, 1 C, CF3), 122.83 (s, 1 C), 122.16 (s, 1 C), 69.81 (s, 2C overlapping), 69.78 (s, 1 C), 69.71 (s, 1 C), 69.61 (s, 1 C), 69.54 (s, 1C), 69.51 (s, 1 C), 68.06 (s, 1 C), 54.36 (s, 1 C), 48.85 (s, 1 C), 48.57 (s, 1 C), 31.36 (s, 1 C), 27.87 (s, 1C), 20.79 (s, 1 C), 18.75 (s, 1 C), 13.21 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.54 (s 3F). ESI (m / z): 568.1989 (C2oH37F3N308S2+, calculated 568.1969). Synthesis of 18. 6.898 g (13.3 mmol) K was combined with 2.304 g (13.5 mmol) L in a 20 mL scintillation vial under argon, then sealed and stirred at 80 °C for 88 h, then removed from heat and ran 8x (dilute to 10 mL in acetone, precipitate in 35 mL Et2<D, centrifuge, decant buoyant phase). Then, added 12.5 g silica gel, stirred for 12 h in EtOAc to encourage adsorption, added the crude product-silica slurry to a column packed in EtOAc, and purified by silica gel column chromatography using a gradient EtOAc 3:1 EtOAc:acetone eluent, removed most solvent via rotary evaporator, dried over MgSO4, then removed remaining solvent via vacuum oven (115 °C) to afford 18 as an amber oil in 3.48 g (42 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 9.11-9.02 (m, 1 H), 7.79-7.69 (m, 2H), 4.43-4.32 (t, 4H), 3.83-3.74 (q, 4H), 3.59-3.44 (br m, 14H), 3.44-3.35 (br m, 4H), 3.25-3.19 (s, 3H), 3.02-2.94 (m, 2H), 1.77-1.65 (m, 2H), 1.63-1.51 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 136.66 (s, 1 C, aromatic), 125.01-115.33 (q, 1 C, CF3), 122.63 (s, 1 C, aromatic), 122.49 (s, 1 C, aromatic), 71.09 (s, 1 C), 69.83 (s, 2C overlapping), 69.79 (s, 1C), 69.73 (s, 1 C), 69.63 (s, 1 C), 69.57 (s, 1C), 69.52 (s, 1 C), 69.40 (s, 1 C), 68.14 (s, 2C overlapping), 58.05 (s, 1 C), 54.38 (s, 1 C), 48.87 (s, 1 C), 48.85 (s, 1 C), 27.88 (s, 1 C), 20.81 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.55 (s, 3F). ESI (m / z): 614.2044 (C2iH39F3N3OioS2+, calculated 614.2023)

[0156] Synthesis of A. 197.6 g (1 .45 moles) 1 ,4-butanesultone was combined with15 mL (194 mmoles) DMF, and 500 mL (6.85 moles) thionyl chloride in a 3 L round-bottom flask fitted with a reflux condenser, a vacuum trap, and a gas scrubber to neutralize the evolved acidic vapor, and heated to reflux for 1 week. Then, the reaction was cooled to 0 °C and quenched by incrementally adding ice while stirring vigorously. When gas stopped evolving, the mixture was returned to 20 °C and washed with 4 x 750 mL reverse osmosis water, dried over MgSC , and concentrated under reduced pressure to afford A (218.9, 69 %) as a yellow oil.1H NMR (400.2 MHz, DMSO-cfe, 8): 3.63-3.52 (t, 2H), 2.71-2.61 (t, 2H), 1 .82-1 .62 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8) 50.89 (s, 1 C), 45.56 (s, 1 C), 31.38 (s, 1 C), 22.50 (s, 1C).

[0157] Synthesis of B-CFs. 218.7 g (1 .14 moles) A was combined with 206.7 g (1 .39 moles) triflamide, 1 L acetonitrile and 36.4 g (302 mmoles) magnesium sulfate, and stirred until triflamide was fully solvated, then cooled to 0 °C while stirring. Then, 675.8 g (4.89 moles) K2CO3 was added incrementally over 2.5 h while maintaining a temperature of 0 °C. The mixture was allowed return to room temperature while stirring for 64 h, then stopped by filtering out solids and blowing off solvent via air stream. The resulting brown paste was washed with 3 x 500 mL Et2<D, then acidified with 800 mL (14 moles) acetic acid and diluted with an additional 800 mL of acetone. The mixture was stirred until all visible solid pieces dissolved, then concentrated under air stream to afford a tan paste. This was washed with 3 x 1 .5 L Et2<D, then taken up in 1 .5 L acetone, basified with 569 g (4.12 moles) K2CO3, and stirred vigorously for 19 hours before filtering out solids and concentrating the filtrate via air stream. The resulting solid was washed with 1 L Et2<D and placed under reduced pressure to afford B-CF3 as a white, crystalline powder (257.5 g, 66 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 3.71-3.59 (t, 2H), 3.06-2.94 (t, 2H), 1.88-1.73 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 124.97-115.30 (q, 1 C), 53.69 (s, 1 C), 44.97 (s, 1 C), 30.63 (s, 1 C), 21.31 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.49 (s, 3F). ESI (m / z): 301.9545 (C5H8CIF3NO4S2-, calculated 301.9530).

[0158] Synthesis of B-C4F9. A (40 g of 86 wt % solution in acetonitrile, 180 mmoles) was combined with 30.374 g (102 mmoles) M and 100 mL acetonitrile, then stirred until M was solvated. Then, the reaction was cooled to 0 °C under argon and 60.8 g (440 mmoles) K2CO3 was added. The reaction was allowed to return to room temperature while stirring for 96 h, then the solids were removed by filtration. The filtrate was concentrated under air stream, washed with 4x100 mL of dichloromethane, and placed under vacuum to afford B-C4F9 as a tan powder (40.6 g, 88 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 3.70-3.60 (t, 2H), 3.06- 2.95 (t, 2H), 1.89-1.75 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 120-105 (br m, 4C, fluorinated), 53.97 (s, 1 C), 44.95 (s, 1 C), 30.65 (s, 1C), 21.32 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -80.49 (m, 3F), -112.90 (m, 2F), -120.99 (m, 2F), -125.72 (m, 2F). ESI (m / z): 451 .9455 (C8H8CIF9NO4S2-, calculated 451.9434).

[0159] Synthesis of C. 10.00 g (73.2 mmoles) 6-chloro-1 -hexanol was combined with 10.45 g (82.9 mmoles) sodium sulfite and deionized water (56.35 g) and refluxed at 120 °C for 24 h before removing water via air stream at 90 °C and washing the resulting white powder with 4 x 40 mL MeOH. MeOH was removed from the combined washes via air stream, then the resulting white solid was crushed and placed under reduced pressure to afford C as a white powder in 11 .3 g (76 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 3.40-3.32 (t, 2H), 2.47-2.39 (m, 2H), 1.62-1.49 (m, 2H), 1.45-1.34 (m, 2H), 1 .34-1.19 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 60.77 (s, 1C), 51.49 (s, 1 C), 32.47 (s, 1 C), 28.38 (s, 1 C), 25.43 (s, 1 C), 25.11 (s, 1C). ESI (m / z): 181.0541 (C6H13O4S-, calculated 181.0529).

[0160] Synthesis of D. 16.9 g (82.8 mmoles) C was dried via azeotropic distillation of toluene (100 mL), then combined with dry DMF (8.5 mL, 110 mmoles) and thionyl chloride (60 mL, 823 mmoles) under argon in a 500 mL round-bottom flask fitted with a reflux condenser, a vacuum trap, and a gas scrubber to neutralize the evolved acidic vapor. Then, the mixture was stirred at 20 °C for 15 minutes before heating to reflux. After 27 h, an additional 60 mL (823 mmoles) of thionyl chloride was added and the reflux continued for another 21 h before returning to room temperature, cooling to 0 °C, and quenching excess thionyl chloride by incremental addition of ice with vigorous stirring. The mixture was returned to 20 °C and extracted into 3 x 100 mL of Et2<D, then the combined organic washes were dried over MgSO4 and concentrated under vacuum to afford crude D as a yellow oil (22.4 g, exceeding theoretical yield due to impurities).1H NMR (400.2 MHz, DMSO-cfe, 8): 3.60-3.50 (t, 2H), 2.70-2.60 (m, 2H), 1.72-1.50 (m, 4H), 1.42-1.24 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 51.57 (s, 1 C), 45.63 (s, 1 C), 32.29 (s, 1 C), 27.60 (s, 1C), 26.35 (s, 1 C), 24.63 (s, 1 C).

[0161] Synthesis of E. 22.4 g (102 mmoles) crude D was combined with triflamide (18.3 g, 123 mmoles), 4.02 g (33.3 mmoles) MgSC , and 100 mL acetonitrile in a 500 mL round-bottom flask. Then, the reaction was started by adding 59.3 (429 mmoles) of K2CO3. After stirring at 20 °C for 24 h, the solids were removed by filtration and solvent evaporated via air stream. Then, the mixture was washed with 3 x 100 mL of Et2<D, re-diluted to 200 mL in acetone, and acidified by adding 17.5 mL (306 mmoles) glacial acetic acid. The solvent was then evaporated via air stream and the crude mixture washed with another 3 x 100 mL Et2<D, re-dissolved in acetone, filtered to remove solid precipitate, and basified with 34.6 g (250 mmoles) of K2CO3. The mixture was stirred vigorously for 18 h, then solids were removed by filtration and concentrated via air stream to afford E as a tan powder (20.82 g, 55 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 3.67-3.58 (t, 2H), 3.00-2.90 (m, 2H), 1.77-1 .59 (m, 4H), 1.44-1.31 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 124.99-115.32 (q, 1 C), 54.38 (s, 1 C), 45.28 (s, 1 C), 31.82 (s, 1 C), 26.91 (s, 1 C), 25.89 (s, 1 C), 23.54 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.53 (s, 3F). ESI (m / z): 329.9856 (C7H12CIF3NO4S2-, calculated 329.9843).

[0162] Synthesis of F. 22.6 g (251 mmoles) 1 ,4-butanediol was added to a dry, 250 mL round-bottom flask under argon atmosphere and dried by azeotropic distillation with toluene. Then, 50 mL (50 mmoles) 1 M f-BuOK in THF was added dropwise over 20 minutes, followed by 1 ,3-butanesultone (7.10 g, 58.1 mmoles). The reaction was allowed to stir for 2 h at room temperature before diluting in 150 mL acetone and filtering to collect solids. These were washed with 2x100 mL acetone, then placed under vacuum to remove trace solvent to afford 11 .4 g (91 %) of F as a powdery white solid.1H NMR (400.2 MHz, DMSO-cfe, 8): 4.43- 4.38 (t, 1 H), 3.42-3.29 (m, 6H), 2.59-2.43 (m, 2H), 1 .88-1 .71 (m, 2H), 1 .60-1 .34 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 69.93 (s, 1 C), 69.23 (s, 1 C), 60.68 (s, 1 C), 48.50 (s, 1 C), 29.36 (s, 1 C), 26.00 (s, 1 C), 25.69 (s, 1 C). ESI (m / z): 211.0647 (C7H15O5S-, calculated 211 .0635).

[0163] Synthesis of G. 11 .1 g (44.3 mmoles) F was azeotropically distilled with toluene in a 250 mL round-bottom flask fitted with a reflux condenser, a vacuum trap, and a gas scrubber to neutralize acidic vapor. Then, thionyl chloride (64 mL, 877 mmoles) and DMF (4.5 mL, 58.1 mmoles) were added and the solution refluxed at 80 °C for 48 h before cooling to 0 °C and quenching by gradual addition of ice pellets. Crude product was extracted into 3x50 mL of diethyl ether and the combined organic washes were dried over MgSO4 and concentrated under vacuum to afford crude G as a yellow oil in 12.6 g (100%) crude yield.1H NMR (400.2 MHz, DMSO-c / 6, 8): 3.65-3.57 (t, 2H), 3.44-3.29 (m, 4H), 2.69-2.60 (m, 2H), 1.86-1.67 (m, 4H), 1.62-1 .52 (m, 2H).13C NMR (100.6 MHz, DMSO-c / 6, 8): 69.34 (s, 1 C), 68.83 (s, 1 C), 48.63 (s, 1C), 45.54 (s, 1 C), 29.40 (s, 1 C), 26.82 (s, 1C), 25.35 (s, 1 C).

[0164] Synthesis of H. 12.6 g (50.6 mmoles) crude G was combined with 53 mL acetonitrile, 3.255 g (27.0 mmoles) MgSC , and 9.45 g (63.4 mmoles) triflamide in a 250 mL round-bottom flask and stirred until a homogeneous white dispersion. Then, K2CO3 was incrementally added and then the mixture was allowed to stir for 24 h at 20 °C. The solids were removed by filtration and washed with acetone. The filtrate and acetone washes were combined and solvent was removed via air stream. The resulting tan solid was washed with hexanes and passed over a plug of silica (40 g silica, acetone eluent), then combined with 7.4 mL (129 mmoles) acetic acid, concentrated via air stream, and washed with 3x50 mL Et2<D. The product was purified by flash column chromatography (silica gel stationary phase, EtOAc eluent) and concentrated under reduced pressure to afford H (8.5 g, 42 %) as a soft brown solid.1H NMR (400.2 MHz, DMSO-C / 6, 8): 3.68-3.61 (t, 2H), 3.47-3.40 (t, 2H), 3.40-2.94 (t, 2H), 3.03-2.94 (m, 2H), 1.93-1.82 (m, 2H), 1.82-1.71 (m, 2H), 1.66-1.55 (m, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 124.97-115.29 (q, 1 C), 69.04 (s, 1 C), 68.14 (s, 1 C), 51.78 (s, 1C), 45.31 (s, 1 C), 29.10 (s, 1 C), 26.53 (s, 1 C), 24.29 (s, 1 C).19F NMR (376.5 MHz, DMSO-c / 6, 8): -77.53 (s, 3F). ESI (m / z): 359.9980 (C8H14CIF3NO5S2-, calculated 359.9949).

[0165] Synthesis of I. 430.6 g (2.22 moles) TetrEG, 60.2 g (442 mmoles) 1 ,4-butanesultone, and 440 mL THF were combined in a 3 L round-bottom flask and stirred until homogeneous. The mixture was cooled to 0 °C under argon and the reaction was started by adding 75.3 g (1 .34 moles) KOH. The reaction was allowed to return to 20 °C over 24 h, then cooled again to 0 °C and quenched by adding 83.2 g (1 .39 moles) glacial acetic acid. The crude product mixture was washed with 2x1 L hexanes and 3x1 L EtOAc before purifying via flash column chromatography (gradient eluent THF 2:1 EtOAc:acetone) and concentrating via rotovap and then vacuum oven (100 °C) to afford I as a faintly amber solid in 133.5g (82 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 3.63-3.30 (m, 18H), 2.62-2.52 (m, 2H), 1.68-1.48 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 72.37 (s, 1 C), 70.09-69.52 (m, 7C), 60.25 (s, 1 C), 51.20 (s, 1 C), 28.34 (s, 1 C), 21.70 (s, 1 C). ESI (m / z): 329.1281 (C12H25O8S, calculated 329.1265).

[0166] Synthesis of J. 133.5 g (362 mmoles) I was combined with 22 mL (284 mmoles) DMF in a 3 L roundbottom flask under argon. The flask was fitted with a reflux condenser with a gas outlet routed through a vacuum trap and a gas scrubber composed of a glass sparger submerged in 5 L of 5M KOH to prevent release of concentrated acid vapor. Then, 500 mL (5.5 moles) thionyl chloride was added. After the reaction finished bubbling, it was heated to reflux for 72 h before returning to room temperature and quenching by incremental addition of ice pellets with vigorous stirring. After complete quenching of residual thionyl chloride, another 100 mL of water was added and the mixture was stirred vigorously for 20 minutes before extracting with 3x 500 mL Et2<D. The extracted organic phase was transferred to a 3L round-bottom flask with 51 g (42.4 mmoles) MgSO4 and concentrated under reduced pressure before purifying via silica gel column chromatography (silica gel stationary phase, gradient eluent hexanes 4:1 Et2O:hexanes) and concentrating under reduced pressure to afford J in 64.2 g (48 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 3.74-3.61 (m, 4H), 3.61 -3.41 (m, 12H), 3.41-3.31 (m, 2H), 2.68-2.57 (m, 2H), 1.69-1.49 (m, 4H).13C NMR (100.6 MHz, DMSO-cfe, 8): 70.61 (s, 1 C), 70.05-69.55 (q, 7C), 51.20 (s, 1 C), 43.65 (s, 1 C), 28.27 (s, 1 C), 21.58 (s, 1C).

[0167] Synthesis of K. 64.2 g (175 mmoles) J was combined with 31.35 g (210 mmoles) triflamide, 30.8 g (256 mmoles) MgSC , and 174 mL acetonitrile under argon. The mixture was stirred until triflamide was solvated, then cooled to 0 °C and 101 .5 g (735 mmoles) K2CO3 was added to start the reaction. The mixture was allowed to return to room temperature over 24 hours, then stirring stopped to allow the mixture to settle. Then, the liquid phase was decanted through a vacuum filtration apparatus and the solids washed with acetone until the wash solution came away colorless. The combined liquid phase and acetone washes were acidified with 36 mL (630 mmoles) AcOH and concentrated under reduced pressure. Then the mixture was washed with 3x300 mL hexanes and 5x300 mLEt2O. Due to product precipitation during the Et2<D washes, they were stirred vigorously in a round-bottom flask (rather than shaking in a separatory funnel); then the stir bar was stopped to allow phase separation, to decant the buoyant phase. The crude product was then dissolved in EtOAc, then 164 g silica gel was added and the mixture stirred for 12 h before adding the slurry to the top of a silica gel column and purifying with a gradient eluent (EtOAc acetone). The product fractions were concentrated under reduced pressure and basified by adding 25.3 g (183 mmoles) K2CO3 and 2.23 g (19 mmoles) MgSO4 and stirring vigorously for 12 hours before filtering out solids, washing solids with acetone, combining product solution and acetone washes, concentrating under reduced pressure, and precipitating in Et20 to afford K as a tan powder in 42.8 g (47 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 3.75-3.63 (m, 4H), 3.61-3.43 (m, 12H), 3.43-3.34 (t, 2H), 3.02-2.91 (m, 2H), 1 .77-1 .63 (m, 2H), 1 .63-1 .52 (m, 2H).13C NMR (100.6 MHz, DMSO- d6, 8): 125.46-115.78 (q, 1 C), 70.99-69.95 (m, 8C), 54.81 (s, 1 C), 44.03 (s, 1 C), 28.35 (s, 1 C), 21 .21 (s, 1 C).19F NMR (376.5 MHz, DMSO-cfe, 8): -77.50 (s, 3F). ESI (m / z): 478.0601 (C13H24CIF3NO8S2-, calculated 478.0578). Synthesis of L. 10.059 g (148 mmoles) imidazole was stirred in 125 mL acetonitrile until fully dissolved, affording a clear, colorless solution. Then, 41 .289 g (736 mmoles) KOH was added and allowed to stir for 25 minutes, affording a colorless, opaque mixture., followed by 30.832 g (168 mmoles) MEE-Br was added dropwise over 5 minutes to start the reaction. The mixture was allowed to stir for 24 h at 20 °C before decanting the yellow product solution, concentrating via air stream while stirring over MgSO4, and then purified by flash column chromatography (silica gel stationary phase, gradient EtOAc 6:1 EtOAc:MeOH eluent) and concentrated under reduced pressure to afford L as an amber oil in 23.232 g (92 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 7.62-7.56 (s, 1 H), 7.18-7.13 (m, 1 H), 6.89-6.84 (m, 1 H), 4.13-4.07 (t, 2H), 3.69-3.63 (t, 2H), 3.53-3.48 (m, 2H), 3.44-3.38 (m, 2H), 3.25-3.20 (s, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 137.47 (s, 1 C), 128.12 (s, 1 C), 119.60 (s, 1 C), 71.19 (s, 1 C), 69.81 (s, 1 C),

[0168] 69.44 (s, 1 C), 58.08 (s, 1 C), 45.95 (s, 1C).ESI (m / z): 171.1147 (C8Hi5N2O2+, calculated 171.1128).

[0169] Synthesis ofM. 254.55 g (843 mmoles) perfluorobutanesulfonyl fluoride was added to a 3 L round-bottom flask. Then, 1 L of 1 M Li-HMDS in THF was added by cannula transfer with vigorous stirring over 6 h and allowed to stir for 24 h before reducing the volume to -500 mL via air stream. Then, 700 mL of 6 N HCI was added over the course of 1 day. The organic phase was collected, then the aqueous phase washed with 4x 75 mL of Et2O; the organic phase and Et2O washes were combined and stirred over anhydrous sodium sulfate and activated charcoal, stirred for 24 h, and passed over a plug of celite and concentrated by stirring under reduced pressure to afford M as a tacky brown-orange powder in 233 g (92 %) yield.1H NMR (400.2 MHz, DMSO-c / 6, 8): 9.26-8.99 (s, 2H).13C NMR (100.6 MHz, DMSO-cfe, 8): 121.6-104.6 (br m, 4C).19F NMR (376.5 MHz, DMSO-cfe, 8): -80.56 (m, 3F), -114.18 (m, 2F), -121.28 (m, 2F), -125.89 (m, 2F). ESI (m / z): 297.9594 (C4HF9NO2S-, calculated 297.9579).

[0170] Synthesis of N. 13.075 g (159 mmoles) 2-methylimidazole, 23.958 g (175 mmoles) 1 -bromobutane, and 80 mL THF were combined in a 250 mL round-bottom flask and stirred until homogeneous. 22.632 g (403 mmoles) KOH was added to start the reaction, the mixture was stirred for 17 h at 20 °C, and the solvent removed via forced air stream over 3 h. The resulting red oil was decanted and the remaining solids washed with 4 x 30 mL Et20. The decanted oil and Et20 washes were combined and dried over MgSO4, then centrifuged, decanted, and concentrated under reduced pressure. The resulting brown oil was extracted into 4x70 mL hexanes and concentrated under reduced pressure to afford N as a brown oil in 18.541 g (37 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 7.04-6.97 (d, 1 H), 6.75-6.67 (d, 1 H), 3.89-3.78 (t, 2H), 2.30-2.21 (s, 3H), 1.67-1.55 (m, 2H), 1.32-1.19 (m, 2H), 0.94-0.83 (t, 3H).13C NMR (100.6 MHz, DMSO-C / 6, 8): 143.90 (s, 1 C), 126.57 (s, 1C), 119.89 (s, 1 C), 45.32 (s, 1 C), 32.80 (s, 1 C), 19.68 (s, 1 C), 13.91 (s, 1 C), 13.02 (s, 1 C). ESI (m / z): 139.1236 (C8HI5N2+, calculated 139.1230).

[0171] Synthesis of O. 1.012 g (12.3 mmoles) 2-methylimidazole was combined with 2.488 g (13.6 mmoles) MEE-Br and 12.2 mL acetonitrile and stirred until homogeneous. The reaction was started by adding 1 .860 g (33.1 mmoles) KOH and allowed to stir at 20 °C for 18 h before centrifuging to remove solids, concentrating under reduced pressure, washing with 3x2 mL hexanes, and extracting into 5x3 mL Et20 to afford O as a brown oil in 1.1 g (48 %) yield.1H NMR (400.2 MHz, DMSO-cfe, 8): 7.05-7.01 (d, 1 H), 6.73- 6.68 (d, 1 H), 4.05-3.97 (t, 2H), 3.68-3.60 (t, 2H), 3.51 -3.46 (m, 2H), 3.44-3.37 (m, 2H), 3.24-3.19 (s, 3H), 2.29-2.25 (s, 3H).13C NMR (100.6 MHz, DMSO-cfe, 8): 144.07 (s, 1C), 126.02 (s, 1 C), 119.78 (s, 1 C), 71.24 (s, 1 C), 69.86 (s, 1 C), 69.61 (s, 1C), 58.10 (s, 1 C), 45.23 (s, 1 C), 12.66 (s, 1 C). ESI (m / z): 185.1288 (C9Hi7N2O2+, calculated 185.1285)

[0172] Synthesis of 28. 1 -allylimidazole (10.797 g, 99.8 mmoles), 11 -bromo-1 -undecanol (25.165 g, 100.2 mmoles) and BHT (290 mg, 1 .32 mmoles) were combined in a 500 mL round-bottom flask under argon, then heated to 65 °C with stirring for 24 h. The crude product was broken into a powder, then washed with ethyl acetate and placed under reduced pressure to afford 28 and as a faintly yellow solid (33.91 g, 95 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.32-9.24 (s, 1 H), 7.90-7.80 (s, 1 H), 7.80-7.72 (s, 1 H), 6.14-5.98 (m, 1 H), 5.39-5.32 (m, 1 H), 5.32-5.23 (m, 1 H), 4.90-4.82 (m, 2H), 4.41-4.28 (s, 1 H), 4.23-4.13 (m, 2H), 3.45-3.26 (m, 2H), 1.84-1.73 (m, 2H), 1 ,44-1.35 (m, 2H), 1.33-1 .15 (m, 14H).

[0173] Synthesis of 29. 28 (1g, 2.78 mmoles) was combined with 1 ,4-butanesultone (383 mg, 2.18 mmoles), DIPEA (367 mg, 2.84 mmoles) and BHT (9 mg, 0.04 mmoles) were combined in a 20 mL scintillation vial and heated to 80 °C with stirring for 4.5 days, then recrystallized in acetone, washed 2x in acetone, recrystallized from 2 mL DMSO, then washed 2x with DMSO and 1x with acetone before removing residual solvent under reduced pressure to afford 29 as a white powder (169 mg, 14 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.36-9.08 (s, 1 H), 7.96-7.59 (m, 2H), 6.17-5.92 (m, 1 H), 5.49-5.13 (m, 2H), 5.00-4.68 (m, 2H), 4.30-4.04 (m, 2H), 3.47-3.15 (m, 4H, overlapping with water peak), 2.43-2.30 (m, 2H), 1.87-1.71 (m, 2H), 1 .68-1.40 (m, 6H), 1.36-1.14 (m, 14H). ESI (m / z): 415.2609 (C9Hi7N2O2+, calculated 415.2625)

[0174]

[0175] Synthesis of 30. 5 (511 mg, 0.926 mmoles), poly(mercaptopropylmethyl siloxane) (PMMS, 153 mg, 1.14 mmoles, thiol basis), 2-hydroxy-2-methylpropiophenone (26 mg, 0.158 mmoles), DMF (500 mL), and THF(500 mL) were combined in a 10 mL round-bottom flask, homogenized by sonicating for 10 minutes, then degassed by bubbling with dry argon while stirring for 5 minutes. The reaction mixture was then irradiated at 50 mW cm2(Jmax= 365 nm) for 20 minutes while stirring. Then, the crude reaction mixture was purified by 5x (dilution to 2 mL in acetone, homogenizing by vortex and sonication, precipitation in 12 mL of Et2<D, vigorous shaking, and centrifugation to accelerate phase separation), then residual solvent was removed via vacuum oven (3.5 h, 55 °C) to afford 30 as a clear, yellow, viscous polymer melt (654 mg, 98 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.15-9.04 (s, 1 H), 7.83-7.69 (s, 2H), 4.43-4.15 (m, 4H), 3.85-3.71 (m, 2H), 3.59-3.43 (m, 12H), 3.41-3.34 (m, 2H), 3.03-2.91 (t, 2H), 2.61-2.35 (m, 4H), 2.10-1.99 (m, 2H), 1 .76-1.64 (m, 2H), 1.62-1.47 (br m, 4H), 0.68-0.52 (s, 2H), 0.13-0.01 (s, 3H).

[0176] Synthesis of 31 . 5 (4.02 g, 7.29 mmoles), PMMS (1 .084 g, 8.07 mmoles, thiol basis), 2-hydroxy-2- methylpropiophenone (220 mg, 1 .34 mmoles), DMF (4 mL), and THF (4 mL) were combined in a 20 mL round-bottom flask, homogenized by sonicating for 10 minutes, then degassed by bubbling with dry argon while stirring for 15 minutes. The reaction mixture was then irradiated at 50 mW cm2(Jmax= 365 nm) for 50 minutes while stirring. Then, the crude reaction mixture was purified by washing with 1x 30 mL hexanes, 3x 30 mL Et2<D, 2x 25 mL acetone, and 1x 30 mL Et2<D before concentrating in vacuum oven for 9 h at 55 °C to afford 31 as a clear, yellow, viscous polymer melt (3.8 g, 74 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.14-9.04 (s, 1 H), 7.80-7.70 (s, 2H), 4.43-4.18 (m, 4H), 3.84-3.73 (m, 2H), 3.61-3.42 (m, 12H), 3.42-3.25 (m, 2H), 3.05-2.90 (m, 2H), 2.58-2.38 (m, 4H), 2.12-1.98 (m, 2H), 1.78-1.63 (m, 2H), 1 .63-1 .45 (m, 4H), 0.69-0.50 (m, 2H), 0.16- -0.03 (m 3H).

[0177] Synthesis of 32. 5 (589 mg, 1.07 mmoles), PMMS (139 mg, 1.04 mmoles, thiol basis), 2,2-dimethoxy-2- phenylacetophenone (46 mg, 0.179 mmoles), DMF (500 mL), and THF (500 mL) were combined in a 10 mL round-bottom flask, homogenized by sonicating for 10 minutes, then degassed by bubbling with dry argon while stirring for 10 minutes. The reaction mixture was then irradiated at 50 mW cm-2(Jmax= 365 nm) for 20 minutes while stirring. Then, the crude reaction mixture was purified by washing with 3x 14 mL Et20, then 3x (dilution to 2 mL in acetone, homogenizing by vortex and sonication, precipitation in 12 mL of Et20, vigorous shaking, centrifugation, and decanting the buoyant phase), then residual solvent was removed via vacuum oven (3.5 h, 55 °C) to afford 32 as a clear, yellow, viscous polymer melt (500 mg, 69 %).1H NMR (400.2 MHz, DMSO-cfe, 8): 9.17-8.96 (m, 1 H), 7.84-7.62 (m, 2H), 4.40-4.12 (m, 4H), 3.85- 3.64 (m, 2H), 3.57-3.38 (m, 12H), 3.38-3.30 (m, 2H), 2.99-2.87 (m, 2H) 2.45-2.37 (m, 2H), 06-1.95 (m, 2H), 1.73-1.59 (m, 2H), 1.58-1.43 (m, 4H), 0.66-0.44 (s, 2H), 0.14-0.10 (s, 3H).

[0178] EXAMPLE 2:

[0179] Varying the length and composition of Rb has a notable effect on the melting and solidifying properties of the zwitterionic liquid. FIG. 2 shows changes in the melting (Tm) and solidifying (Tg, glass transition temperature) of zwitterionic liquids containing the same RY, Y, X, and Rx groups, but variations on the length and constituents of the Rb group. Tgdecreases as a function of increasing spacer length and increasing heterogeneous chain constitution of the zwitterionic liquid. Tmincreases with increasing spacer length for a pure alkyl spacer, but diminishes dramatically upon the inclusion of heteroatoms into the spacer to afford room-temperature liquids with much longer spacers than accessible with alkyl spacers alone. Further tests show, in FIG. 3, that the frequency-dependent relative permittivity varies between three of the zwitterionic liquids (4, 8, and 16-atom spacers) for which Tmand Tgwere measured, indicating a correlation between Rb length and constitution and various physical properties. In addition, thermal data (Tm, Tg, AHm, ASm) for all compounds was measured (FIG. 4) for direct comparisons between their physical properties.

[0180] The impact of the tail Rt on the melting points of four classes of zwitterions (ZIs) is shown in FIG. 5A, where melting points Tmare shown as relative values compared with structures featuring Rt = butyl; absolute Tmand thermodynamic parameters are provided in FIGS. 6A-6D. Zwitterions with n-butyl intercharge spacers and a CFs-sulfonimide anion exhibit a monotonic decrease in Tmfollowing the series Tm, methyl > Tm, ethyl > Tm, butyl > Tm, aiiyi, which is accompanied by a concomitant decrease in their respective enthalpy of fusion. Across this series, ATmranged from +77 °C (methyl) to -16 °C (allyl) compared to butyl (reference). Methoxyethoxyethane (MEE) and allyl tails were consistently lower-melting than butyl across three other classes of ZIs, including those with an n-butyl spacer and a sulfonate anion (Tm,aiiyi = Tm, butyl - 53 °C and Tm, MEE — Tm, butyl ~ 80 C), n-butyl spacers with CFs-sulfonimide anions and R2 - methyl ( / MEE = Tm,butyi - 58 °C), and an n-hexyl spacer with a CFs-sulfonimide anion, where Tm, MEE was not quantified because the isolated liquid does not crystallize. Together, these observations indicate that the alkyl series results in a decrease in Tmprimarily due to enthalpic effects (FIGS. 6A-6D). The steric hindrance of the cation informs this result, and this expectation is in good agreement with melting point trends in conventional ionic liquids (ILs).While the allyl group is shorter than butyl, it affords a lower Tm, possibly due to cation coordination by the electron-rich p-bond. By contrast, MEE tails offer entropy-dominated Tmdepression compared to a butyl tail.

[0181] Next, the Tmof two classes of zwitterions was measured as a function of substitution at R2 (FIG. 5B). All species contained a CFs-sulfonimide anion and an n-butyl inter-charge spacer. For molecules with an n- butyl tail, replacement of the reference methyl group with a proton at R2 led to a 59 °C decrease in Tm. However, this effect is less pronounced with an MEE tail; a proton at R2 only produced a 5°C decrease in Tmcompared to the methyl reference. To better understand these effects, the corresponding melt thermodynamic data was analyzed (FIGS. 7A-7B). In each case, both AHmand ASmincreased upon substituting a methyl group with a proton. The observed decrease in Tmis attributed to a relatively larger change in ASm- This trend is consistent with prior studies of imidazolium ionic liquids, which have shown that the anion strongly interacts with the proton at R2. The substitution of a methyl group eliminates that interaction, decreasing AHm- Similarly, larger ASmwith proton substitution at R2 is consistent with conventional imidazolium ILs, for which two mechanisms are hypothesized: (1) hydrogen bond-mediated ion pair conformers and (2) modified barrier to rotation at the 1 and 3 positions.

[0182] The Zl thermal behavior was characterized as a function of spacer length and composition. The relative Tmof 4-carbon-spacer reference molecules against 6-, 8-, and 16-atom spacer analogs are shown in FIG. 5C. All ZIs synthesized with 8- and 16-atom spacers are liquids at room temperature. A 6-carbon spacer affords a liquid with an MEE tail and a crystalline solid with a butyl tail; all ZIs with 4-carbon spacers are crystalline solids. The six liquids (ZILs 13-18) remained transparent with no signs of crystal formation for at least 6 months at ~22°C. Moreover, these ZILs underwent vitrification rather than crystallization during a cool-heat cycle, which prevented analysis of their melting behavior via DSC. Tgexhibits a consistent negative correlation with spacer length across all classes of ZIs synthesized here, decreasing by 11 -21 °C with increasing space length (FIG. 8A). The change in heat capacity (ziCg) at Tgwas used to better understand the Zl energy landscape in the liquid state. For each DSC scan, the liquid (Cg / ,q) and glass (Cg g / ) heat capacities at Tgwere estimated by extrapolating the linear regions of the thermogram on either side of the transition. ACg= Cgnq- Cg giwas then calculated on both specific (ACgs, FIG. 8B) and molar (ziCgm, FIG. 8C) bases, and it was found that ACgshowed a strong positive relationship with spacer length and flexibility. The molar capacities were plotted against each molecule’s glass transition temperature as well (FIG. 8D). One explanation is that a molecule with more rotatable bonds can access a broader range of structural and vibrational modes. However, it is striking that this trend holds on a specific basis, since it implies a net gain in available states despite fewer molecules per unit mass.

[0183] Analyzing the melting behavior of ZIs with 4- and 6- atom spacers offers further insight into spacerproperty relationships (FIGS. 9A-9C). Zl 8 (four-carbon spacer) melted at 73 °C, well below Zl 12, (six- atom spacer, Tm= 103 °C), driven by AHm. This highlights a major inconsistency - i.e., by increasing the spacer from four to six atoms, ZIs are created with increased Tmhowever, ZIs with eight and sixteen atoms are stable liquids. To understand this, it is observed that the four- and six-atom spacers are straight-chain alkanes, while the 8- and 16-atom spacers contain 1 and 4 ether groups, respectively. This difference has two important implications. First, ether-rich species are more flexible (i.e., have shorter persistence lengths) than straight-chain alkanes, offering greater conformational freedom. Second, prior reports argue that ethers coordinate the imidazolium cation to decrease Tm. Together, these offer a “mixed-mode” hypothesis for the stability of liquids with 8- and 16-atom spacers: long, ether-rich spacers suppress Tmby some combination of enthalpic and entropic mechanisms. As demonstrated below, the spacer strongly impacts their viscosity (h) and dielectric constant (er), making it a critical design parameter for synthesizing ZILs.

[0184] The impact of anion composition Rais quantified across three classes of ZIs. The experiments focused on sulfonyl-derived anions, including a sulfonate (used as a control), CFs-sulfonimide, and C4Fg-sulfonimide (relative TmFIG. 5D, thermodynamic parameters FIGS. 10A-10C). All molecules in this series are crystalline solids at room temperature and featured a 4-carbon spacer and a proton at R2. CF3- sulfonimide is consistently the lowest-melting anion (FIG. 5D, FIGS. 10A-10C), but its influence depends on other functional groups. For example, ZIs with allyl, butyl, and MEE tails melted at 55, 91 , and 15 °C below the sulfonate reference, respectively (FIG. 5D), driven by their relatively lower AHm(allyl, butyl) and higher ASm(MEE). One Zl with C4Fg-sulfonimide was synthesized, and it melted at 2 °C and 57 °C above those with sulfonate and CFs-sulfonimide, respectively (FIG. 5D). This is not surprising given it has comparable ASmand AHmvalues to the sulfonate Zl (FIGS. 10A-10C). This difference cannot be explained in terms of electron-withdrawing strength, since the corresponding (CF3, C4Fg) sulfonic acids exhibit comparable pKa values (0.7 in acetonitrile). However, their higher Tmis consistent with prior reports that indicate strong interactions between fluorine atoms in C4Fg-sulfonimide and 1 -ethyl-3- methylimidazolium counterions.

[0185] EXAMPLE 3:

[0186] Seven ZIs were selected for rheological characterization. These include five ZILs (13, 14, 15, 17, and 18 as enumerated in FIG. 4) and two crystalline ZIs (3 and 10 as enumerated in FIG. 4) that are melted and supercooled before each measurement. Zl 3 serves as a control; despite its high Tmof 84 °C, it is the most frequently reported zwitterionic liquid. Each Zl exhibits a low shear plateau viscosity 77 at shear rates, y , below 101s’1, followed by a shear thinning response at higher shear rates (FIG. 11 A). This effect is most pronounced for liquids with higher viscosity, especially the Zl 3 control. Notably, ZILs with functional groups that give rise to the lowest thermal transitions (Tm, Tg) exhibit the lowest apparent viscosity 77. Their?7 at y= 1 s’1is shown as a function of spacer length in FIG. 11 B, which also highlights the roles of anion Raand tail Rt. Comparing supercooled species 3 (sulfonate anion, highest viscosity) and 10 (CFs-sulfonimide, second- highest viscosity), the importance of anion selection is revealed. For example, ZIL 10 is nearly 50-fold less viscous than Zl 3 (control). An additional 10-fold reduction in viscosity is achieved by increasing spacer length to sixteen atoms (ZIL 18), resulting in more than a 500-fold lower viscosity compared to Zl 3 (control).

[0187] Correlations between the thermal properties and room-temperature viscosity of ZILs are highlighted in FIG. 11 C-11 D. Tgcorrelates strongly with viscosity (FIG. 11 C), while ACg,mexhibits the opposite trend (FIG. 11 D). These findings are in good agreement with conventional ionic liquids, in which higher viscosity is attributed to fewer degrees of freedom in the liquid state. Using ACg,mas a rough proxy, a similar trend is observed: increasing length and flexibility in tails and spacers elevates ACg,mand, concomitantly, decreases both 77 and Tg. Consistent with prior reports, anhydrous Zl 3 is observed to crystallize over several weeks under ambient conditions. By contrast, Zl 10, which is roughly ~50-fold less viscous at low shear rates, crystallizes within hours. The viscosities of ZILs 13-18 are roughly 100-500-fold lower than Zl 3 and 2- to 10-fold lower than Zl 10. Yet, the six ZILs remain transparent with no change in properties over a period of at least 6 months after synthesis, purification, and drying, offering strong evidence of their thermodynamic stability.

[0188] Dielectric relaxation spectroscopy was carried out on these same seven ZIs and on silicone oil, an additional control, to understand the impact of Rs, Rt, and Raon their dielectric properties. Specifically, the five ZILs (13, 14, 15, 17, and 18 as enumerated in FIG. 4) and two ZIs (3 and 10 as enumerated in FIG. 4) that are crystalline solids under ambient conditions were evaluated. FIG. 12A shows the unitless relative permittivity of each ZIL as a function of dielectric frequency f = 20 Hz - 2 MHz. In this range, all seven ZIs exhibited a fast relaxation event corresponding to electric field-mediated dipole bias (FIG 12A,i). Their corresponding plateau region is taken as the static dielectric constant. At longer timescales, a slower polarization event is observed, which is attributed to macroscopic electrode charging (FIG. 12A,ii). By contrast, silicone oil exhibits a consistent er~ 2.25-2.38 on experimental timescales, with neither event observed due to its lack of polar groups. FIG. 12B shows dielectric loss tangent tan(t5) as a function of dielectric frequency; the maxima are taken as the relaxation timescales for the polarization events described in FIG. 12A. FIG. 12C shows the static dielectric constants as mean ± 1 standard deviation over plateau regions of polarization event (i), as a function of zwitterion spacer length.

[0189] ZIs 3 and 10 are distinguished solely by their anion composition (sulfonate versus CFs-sulfonimide, respectively). The relaxation timescales (FIG. 12B,i) for bulk polarization revealed by maxima of tan(t5) are 630 ps (Zl 3) and 16 ps (Zl 10), a roughly 40-fold decrease from sulfonate to CFs-sulfonimide that is in good agreement with the measured viscosity (FIGS. 11A-E, ~48-fold difference). This difference in anion composition affords differences both thermal (Tm, ASm, AHm, Tg, ACg,) and kinetic (77, tan( 5) maxima) properties throughout this study. However, it has negligible impact on the static dielectric constant er,s ~ 236 (Zl 3) and 239 (Zl 10, FIG. 12C), whose values agree with prior reports of Zl 3 (S~ 250) within 1 S.D. of our data. Polarization magnitude (S) and timescale (tan( 5) maximum) depend strongly on spacer length. Specifically, longer spacers afford stronger polarization and faster timescales. The MEE series of Zl 10, ZIL 13, ZIL 15, and ZIL 18 shows relaxation timescales of 16 ps, 13 ps, 5 ps, and 2.5 ps, and static permittivity values of 239, 297, 351 , and 411 , respectively. Interestingly, relaxation timescales decrease with increasing spacer length, but the largest decrease is for ZILs with the six- to eight-atom spacer. This finding is consistent with a hypothesis that the more flexible ether decreases thermal transitions and roomtemperature viscosity compared to alkanes. By contrast, the effect of spacer length on the static dielectric constant, sr,s, suggests that spacer length, rather than composition, is the key parameter. ;:rsshows a sublinear dependence on spacer length, supporting a prior report that, at concentrations exceeding polarization volume overlap, permittivity of a zwitterion-rich system undershoots Onsager-like scaling (;:rs~ pap2)- The imidazolium tail Rt showed a modest influence on relaxation timescales, with a ~2-fold decrease in relaxation time when replacing a butyl tail (ZILs 14 and 17) with MEE (ZILs 15 and 18), consistent with the apparent viscosity data for the same ZILs. However, Rt has negligible impact on srs.; with both eight- and sixteen-atom spacers, meanSwhen exchanging butyl (339, 422) for MEE (351 , 411) tails was within one standard deviation (FIG. 12C). ZILs with eight-atom spacers (ZILs 14, 15) show comparable sr,sto the highest-performing reported molecules at -350, while those with sixteen-atom spacers (ZILs 17, 18) represent a -20% improvement.

[0190] There are functional differences between the two types of mass within any zwitterion. Dipole-active moieties, composed of the cation, anion, and inter-charge spacer, contribute directly to the bulk polarizability of ZILs. By contrast, dipole-inactive moieties, composed of pendent functional groups such as the imidazolium tail Rt and 2 position R2, do not contribute to their dipole moment. To date, dipole-inactive moieties have been the primary mode of Tmsuppression in ZIs synthesized by others. However, this carries a penalty: increasing dipole-inactive mass decreases dipole density and bulk permittivity. As an alternative, tuning the inter-charge spacer ( / .e., dipole-active mass) synergistically decreases both Tmand 77 while increasing sr,s. Thus, there is an emerging design principle: longer spacers simultaneously increase dipole moment p and decrease dipole density pd. In the limit of short dipoles (3-9 carbon spacers in prior reports and 4-16 atom spacers in this work), permittivity in neat zwitterionic liquids is dominated by p, so increasing spacer length increases bulk permittivity. While there is a need for new scaling laws to describe this behavior, the / / -dominant regime likely extends beyond a 16-atom spacer, implicating Rsas a parameter for permittivity amplification in zwitterion-derived dielectrics.

Claims

What is claimed is:CLAIMS1. A compound of formula:Ry-Y-Rb-X-Rx, wherein X is a negatively charged functional group, Y is a positively charged functional group, Rb is a linker of at least 3 atoms long, Ry is a C>1 hydrocarbyl or a C>1 heterohydrocarbyl, and Rx is absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl, wherein X comprises a negatively charged N or B atom, Rb is a linker of at least 5 atoms long, Rb is a C>1 heterohydrocarbylene, or Ry is a C>5 heterohydrocarbyl.

2. The compound of claim 1 , wherein X comprises:

3. The compound of claim 1 , wherein Y comprises an optionally substituted positively charged five- or six-membered nitrogen containing heterocyclylene.

4. The compound of claim 1 , wherein Rb comprises a C>3 hydrocarbylene or a C>3 heterohydrocarbylene.

5. The compound of claim 1 , wherein Rb comprises an ether, polyether, thioether, or polythioether.

6. The compound of claim 1 , wherein Rb comprises polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane.

7. The compound of claim 1 , wherein Rb comprises a polymer with a molecular weight between 100 g / mol and 1 ,000,000 g / mol.

8. The compound of claim 1 , wherein Rx comprises a C>1 hydrocarbyl or C>1 heterohydrocarbyl.

9. The compound of claim 8, wherein Rx comprises an ether, polyether, thioether, or polythioether.

10. The compound of claim 8, wherein Rx comprises a terminal reactive group.11 . The compound of claim 10, wherein the terminal reactive group comprises an acrylate, an acrylic acid, an ester, an acetal, a disulfide, an alkene, an alkyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an epoxide, an allyl group, an imide, an aldehyde, an azide, a sulfonic acid, a hydrazine, a ketone, or a vinylsulfone.

12. The compound of claim 1 , wherein RY comprises a C>1 hydrocarbyl or C>i heterohydrocarbyl.

13. The compound of claim 12, wherein RY comprises an ether, polyether, thioether, or polythioether.

14. The compound of claim 12, wherein RY comprises a terminal reactive group.

15. The compound of claim 14, wherein the terminal reactive group comprises an acrylate, an acrylic acid, an ester, an acetal, a disulfide, a dibenzocyclooctyne, a silane, a norbornene, a vinyl group, an amine, a hydroxyl, a carboxylic acid, a thiol, a cyano group, an alkyne, an epoxide, an allyl, an imide, an aldehyde, an azide, a sulfonic acid, a hydrazine, a ketone, or a vinylsulfone.

16. A compound of the following table:, wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000.

17. A polymer comprising a backbone comprising at least two subunits of formula:-RA-Z-RB-, wherein each Z is independently a negatively or positively charged functional group, each RA is independently a C>1 hydrocarbylene, C>1 heterohydrocarbylene, or C>1 heterohydrocarbylene, and each RB is independently a C>1 hydrocarbylene, C>1 heterohydrocarbylene, or C>1 heterohydrocarbylene, and wherein the negatively and positively charged functional groups are present in the polymer in a ratio between 4:5 and 5:4.

18. The polymer of claim 17, wherein the negatively charged functional group comprises:

19. The polymer of claim 17, wherein the positively charged functional group comprises an optionally substituted five- or six-membered nitrogen containing heterocyclylene.

20. The polymer of claim 17, wherein the polymer comprises n subunits of the following table:, wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000.wherein each A independently includeswherein each Rf independently comprisesindependently an integer between 1 and 1000.

22. A polymer comprising a backbone and at least one pendant group of the formula:-Ry-Y-Rb-X-Rx or -Ry-X-Rb-Y-Rx wherein each X is independently a negatively charged functional group, each Y is independently a positively charged functional group, each Rb is independently a linker of at least 3 atoms long, each RY is independently a C>1 hydrocarbylene or a C>1 heterohydrocarbylene, and each Rx is independently absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl.

23. The polymer of claim 22, wherein the backbone comprises polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane.

24. The polymer of claim 22 or 23, wherein X comprises a negatively charged N or B atom, Rb is a linker of at least 5 atoms long, Rb is C>1 heterohydrocarbylene, or RY is C>5 heterohydrocarbyl.

25. The polymer of any one of claims 22-24, further comprising a second pendant group comprising a linking moiety.

26. The polymer of claim 25, wherein the linking moiety is a thiol.

27. The polymer of claim 25, having the formula:wherein n, a, b, and c are integers from 10-1000, and R is heterohydrocarbyl, hydrocarbyl, aryl, heteroaryl, cycloalkyl, polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane.

28. The polymer of claim 22, wherein the pendant group is:

29. The polymer of claim 22, comprising the following structure:, wherein m is an integer between 0 and 19, and n, p and q are independently an integer between 1 and 1000.

30. A polymer comprising a backbone and at least two pendant groups of the formula:-RA-Z-RB, wherein each Z is independently a negatively or positively charged functional group, each RA is independently a C>1 hydrocarbylene or a C>1 heterohydrocarbylene, and each RB is independently absent, a C>1 hydrocarbyl, or a C>1 heterohydrocarbyl, wherein the negatively and positively charged functional groups are present in the polymer in a ratio between 4:5 and 5:4.

31. The polymer of claim 30, wherein the backbone comprises polysiloxane, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polystyrene, polynorbornene, polycyclooctene, polylactam, polylactone, polyethylene glycol, polybutadiene, polyester, polyamide, polyimide, poly(vinylimidazole), poly(vinylimidazolium) or polyurethane.

32. The polymer of claim 30, wherein the negatively charged functional group comprises:

33. The polymer of claim 30, wherein the positively charged functional group comprises an optionally substituted five- or six-membered nitrogen containing heterocyclylene.

34. The polymer of claim 30, wherein the pendant groups are of the following table:, wherein m is an integer between 0 and 19, wherein n, p and q are independently an integer between 1 and 1000, and wherein r is an integer between 0 and 10.

35. A polymer comprising one of the following structures:wherein R comprises a mono- or divalent RAFT agent, wherein Rc comprises, wherein m is an integer between 0 and 19, and n, p, q, and r are independently an integer between 1 and 1000.

36. A block copolymer comprising the polymer of any one of claims 17-35.

37. A cross-linked polymer comprising the polymer of any one of claims 17-35.

38. A dielectric actuator comprising: a) two electrodes; and b) a dielectric material comprising the compound of claims 1-16 or the polymer of any one of claims 17-35 in contact with and separating the two electrodes, wherein, when a voltage is applied to the two electrodes, the dielectric material polarizes in response to the applied electric field generated between the two electrodes to produce a strain.

39. A capacitor comprising: a) two electrodes; and b) a dielectric material comprising the compound of claims 1-16 or the polymer of any one of claims 17-35 in contact with and separating the two electrodes, wherein, when a voltage is applied to the two electrodes, the dielectric material polarizes in response to the applied electric field generated between the two electrodes to store electrical energy.

40. A transistor comprising: a) a source, gate, and drain terminals; and b) a gate dielectric comprising the compound of claims 1-16 or the polymer of any one of claims 17- 35.

41. A hydraulically amplified self-healing electrostatic (HASEL) actuator comprising: a) two electrodes, and b) a dielectric material comprising the compound of claims 1-16 or the polymer of any one of claims 17-35 enclosed inside an elastic shell that is in contact with and separating the two electrodes, wherein, when a voltage is applied to the two electrodes, the enclosed compound polarizes to effect actuation.

42. A battery comprising: a) an anode and a cathode; and b) a solid-state or gel-phase electrolyte comprising the compound of claims 1 -16 or the polymer of any one of claims 17-35 disposed between the anode and the cathode.

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