Polyaniline-based chlorine resistant hydrophilic filtration membranes

FOLVANILINE-BASED CHLORINE RESISTANT HYDROPHILIC FILTRATION MEMBRANES

This application claims die benefit of priority to United States Provisional Patent Application serial number 61/976,688, filed April 8, 2014, which is hereby incorporated by reference in its entirety.

An abundant supply of fresh water is a fundamental requirement: for municipal, industrial and agricultural uses. However, rising populations and source contamination have exerted increasing stress on fresh water supplies. Along with pressure from stricter regulations for clean water, improvements in water treatment technology are critical (Howe, Κ. J, and Tchobanoglous, G, (2005)Water Treatment: Principles and Design, John Wiley & Sons, Ine., Hoboken, New Jersey, 2'" edti.; Service, R. F. (2006)Science313,1088-1090).

Membrane-based filtration is the most important and widely used method for water purification due to its ability to completely and continuously filter impurities by size exclusion on a large scale (Howe, Κ. J. and Tchobanoglous, G. (2005) Water Treatment:

Principles and Design, John Wiley & Sons, lac,, Hoboken, New Jersey, 2ⁿ“ edit).

Generally, membranes can be categorized into four types: mterofiltration. (MF), ultrafiltTation (UF), .nanofiltration (NF) and reverse osmosis (RO) based on their pore size and ability to reject different matter,

UF membranes have an average pore size of-10 nm. In waste water treatment, UF membranes are used to reject pathogenic microorganisms such as viruses, bacteria, protozoa and other colloids (Cheryan, Μ. (1998) Ultrqflltratkm and MicmflUratkm Handbook,Technomic, Lancaster, PA). They can serve as a pretreatment step for desalination (Howe, Κ. J. and Tchobanoglous, G. (2005) Water Treatment: Principles and Design,John Wiley& Sorts, 1π℮,, Hoboken, New Jersey, 2ⁿⁱⁱ edn.; Rosberg, R. (1997)Desalination 1.10,107-114). UF membranes are commonly used for separations in the chemical, pharmaceutical, food and beverage industries, and are an integral component in blood dialysis.

When a membrane is used for separation, the flux gradually decreases during operation as the membrane is fouled by inorganic particulates, organic matter and/or biological microorganisms. The susceptibility to fouling varies among different membrane materials due to hydrophobic interactions between the foulant and the surface of the polymeric membrane. Thus, membrane hydrophiliclty has been linked to a membrane's propensity to foul, t.e. hydrophilic membranes generally foul less titan hydrophobic membranes (Mcverry, Β. Τ., et ai, (2013) Cheat. Mater.25, 3597-3602; Liao, Υ., et ai.

(2014) Materials Horizons 1, 58-64). A more hydrophobic membrane allows fbulanis to adhere strongly via van der Waals interactions to the membrane surface that leads to irreversible membrane fouling (Bilal, Ν., et ai. (2005) Separ. ScLj'edmoL 179, 323-333).

Chemical cleaning is typically used to remove adhered organic matter and biofilms from the membrane surfaces. Cleaning treatments restore membrane performance to regain flux loss during operation due to membrane fouling. Common chemicals used for cleaning membranes include caustics, oxidants/disinfeetants, acids, chelating agents and surfactants (Liu, C,, et al, (2006) Membrane Chemical Cleaning: From Art to Science,Pall Corporation, Port Washington, NY 11050, USA). Chlorine bleach (sodium hypochlorite), is popular in Industry for its low cost, commercial availability and ability to effectively reduce fouling when added to the feed solution. Strong oxidants such as hypochlorite not only kill microorganisms, but also oxidize functional groups in natural organic matter into more water-soluble moieties, allowing the new species to be easily washed away during operation. However, strong oxidants simultaneously attach chemical bonds found within the polymeric membrane material, negatively affecting the membrane properties (Eykamp, W.

(1995) Microfiltration and ultrafiltration. InMembrane Separation Technology: Principles and Application's, Elsevier Science; Amsterdam; Gifis, V„ et al. (2006) J. Membr. Set 276, 185-192: Wietik, I, ML, et al (ℓ995),/. Potym. Set. Pol Chem.33, 49-54; Nystrom, ML and Zhu, Η, (1997) J. Membr. Sci.131, 195-205; Wolff, Η. and Zydney, A. L. (2004)J. Membr. Set 243, 389-399; Zhu, Η. and Nystrom, Μ. (1998)./. Membr. Sci.138, 309-321).

The impact of chlorine cleaning on polyethersulfone (PES) membranes shows that chlorine can actually cause more severe fouling and increase the electronegativity of the membrane after cleaning (Arkhangelsky, Ε., et al. (2007) J. Membr. Sci. 305,176-184;

Rouaix, S., et al. {2006}./. Memhr. Sci.277, 137-147; Gaudichet-Maurm, Ε. and Thominette, F, (2006),/. Membr. Sci282, 198-204). This leads to chain scission of the polymer and deteriorates the mechanical strength of the membrane (Arkhangelsky, Ε., et al. (2007) J, Membr. .Sci.305, 176-184; Thominette, F., et a!. (2006) Desalination200, 7-8;

Kuzmenko, D._f et ah (2005) Desalination179, 323-333). Chemical attack by chlorine on polyamide RO membranes results in membrane failure with enhanced passage of salt and water (Manohar, S, Κ. and Macdiarroid, A. G. (1989)Synthetic Met. 29, 349-356; Langer, j. j. (1990) Synthetic Met.35, 295-300: Shin, J. S., et al. (2005) Synthetic Met.151, 246-255; Shadi, L,, et al (2012}</. Αρρℓ. Polym. Sci.124, 2118-2126). In response, attempts have been made to modify membrane materials in order to make them less susceptible to chlorine degradation. For instance, using a polyamide that contains a tertiary amide instead of a secondary amide results in a chlorine-resistant RO membrane (Scheme I) (Manohar, S. Κ. and Maediarmid, A. G, (1989) Synthetic Metals29, 349-356; Langer, J. J, (1990)Synthetic Metals35,295-300).

Conducting polymers and their derivatives have been extensively examined recently for their potential use in water treatment membranes due to their hydrophilic properties, thermal and chemical stability', low-cost, facile synthesis and ability to be modified by doping (McVerry, Β. Τ., ct al. (2013) Chem. Mater.25, 3597-3602; Liao, Υ., et al. (2014)Materials Horizons1, 58-64; Liao, Υ., et al, (2012) J.ColloidInterf. Sci386, 148-157; Bocchi, V., et al. (1991.)J. Mater. Sci.26, 3354-3355; Price, W. E., et ai. (1999) Synthetic Materials102,1338*1341; Alargova, R. G,, et al. (1998) Colloid Surface A134, 331.-342; Li, Χ., et al. (2008) J. Memhr. Sci320, 143-150; Fan, Ζ., et al (2008)./ Memhr.

Set.310, 402-408; Fan, Ζ., et al. (2008) -J. Memhr. Sci.320, 363-371 ; Zhao, S., et ai. (2011} J. Memhr. Sci.385-386, 251-262; Guillen, G. R., et ai. J. Mater. Chem. (2010) 20, 462.1-4628). As one of the most widely studied conducting polymers, poiyanitiae (Pani) in its emeratdiae oxidation state has been blended with the commercial UF membrane material polysuifone (PSf) to form composite UF membranes with enhanced hydrophilicity and permeability (Fan, Ζ., et al. (2008) J.Membr. Sci.310,402-408; Fan, Ζ,, et al. (2008) J.

Memhr. Sci.320, 363-371; Zhao, S.. et al. (2011)./. Membr. Sci385-386, 251-262;

Guillen, G. R., et al. J. Mater. Chem. (2010) 20, 4621-4628). Pure Pani can also form UF membranes that exhibit permeabilities 10 times higher than commercial PSf membranes, but no bovine serum albumin (BSA) rejection (Guillen, G. R,, et al, J. Mater. Chem. (2010) 20, 4621-4628). By adding a secondary amine such as 4-methyipiperidine (4-ΜΡ) into the Pam casting solution, the rejection of Pani UF membrane increases, while the hydrophilicity decreases. Sulfonated Pani, a derivative of Pani, can be blended with PSf to form UF membranes which have shown excellent hydrophilicity and very high flux restoration after water washing (Meveny, Β. Τ., et al. (2013) Client. Mater.25, 3597-3602).

(Chevalier, J. W.,etai.(ℓΨ)ΐ) Macmmokcuks 25, 3325-3331 ; Yang, D. and Mattes, Β. R. (2002) J.Polym. Set Pol. Phys.40, 2702-27i3; Yang. D. and Mattes, Β. R. (1999) Synthetic Met.101, 746-749; Yang, D., et ai. (2002) Macromolecules35, 5304-5313;

Manohar, S. Κ. and Macdiarmid, A. G. (1989) Symfhefic Met.29,349-356). Among these, u-alkyl Pani is the most common form. However, alkyl groups are hydrophobic, so introducing them into Pani will result in some loss of hydrophilicity.

(PVDF). In order for these membranes to function properly, PVDF must be blended or eopoiymerized with a hydrophilic moiety post membrane formation. While PVDF itself is extremely resilient to acid, base, and chlorine, the hydrophilic group is not. Upon exposure to base or chlorine, as during membrane cleaning, the hydrophilic moiety is hydrolyzed and degraded. Over time, this causes the membrane to become more hydrophobic (fouling prone). In addition, the membrane loses mass and compacts thereby becoming less permeable. Despite the known disadvantages caused by blending the polymer with a hydrophilic group, materials for the preparation of filtration membranes that, wholly circumvent these issues have yet to be reported. Herein, filtration membranes comprising material that is intrinsically hydrophilic and resistant to oxidative damage are described.

described herein, the invention, in one aspect, relates to a filtration membrane comprising a polymer formed by polymerizing a compound having a structure represented by a formula;

Several types of ^-substituted Pani have been reported in the literature Filtration membranes are traditionally produced using poly vinyiidene fluoride

In accordance with the purpose's) of the invention, as embodied and broadly wherein η is selected from 1,2, and 3; wherein each of R^!a, R.*⁰, R^ie, and R^w is independently selected from hydrogen, halogen,-CN, -SR¹⁴’, -OR'¹'¹, -NR^R"¹"¹*,

-NR“^JR²'^4>l-r, -SOjR'''\ -(C^:::0)R^x4, and C1-C3 alkyl substituted with 0, Κ 2, or 3 groups selected from halogen, -CN, -SR²⁽⁾, -OR^-NR^R²²*, -SO^R²⁵, and-(O0)R²⁴;

wherein each of R²ⁱ’ and R^2i> is independently selected from hydrogen, halogen, -CN,

-SR³⁰, -OR⁵’, -NR^52aR^S2h, -NR^tt*R^3a>H⁰; -SCfrR³⁵, -(C-O)R³⁴, and C1-C3 alkyl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, -SR'¹⁰, -OR⁷',

-NR/'^;aR^J'^:\ - SCAR'⁵, and -(€=0)Κ^; wherein each of R^JS, R'^>b, and R'¹' is independently selected from hydrogen, halogen, -CN, -SR⁴⁰, -OR^4J,-NR^42aR^42b, -NR^42aR^42bH\ 1-SOjR4^3, and -(O0)R⁴⁴; wherein at least one of R²\ R^2b, R^5a, R^Jb, and R* is not hydrogen; wherein each of R²⁰, R²ⁱ, R^22a, R²²⁰, R^:tb, R^5{, R^&, R^32b, R⁴⁰, R⁴⁵, R^42a, and R⁴²⁰, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and C1.-C3 poiyhaloalkvl; wherein each of R²³and R"⁴, when present, is independently selected fh>m-O^-OR^, C1-C3 alkyl, C1-C3 monohaloalkyl, C1-C3 ipolyhaloalkyl, and -NR^R²**; wherein each ofR²⁵, R^2<w, and R"^:b!\ when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl; wherein each of R” and R'⁴, when present, is independently selected from

-O',-OR⁵⁵, C1-C3 alkyl, C1-C3 monohaloalkyl, CI-C3 polyhaloalkyl, and-NR^MaR^36b;

wherein each of R”, R'^>6a, and R:’⁶'¹, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and C i -C3 polyhaloalkyl; wherein each of R^4-’ and R⁴⁴, when present, is independently selected from -O', -OR⁴⁵, C1-C3 alkyl. Cl -C3 monohaloalkyl, C1-C3 polyhaloalkyl, and -NR⁴⁰³R^4<a!; and wherein each of R⁴⁵, R⁴**, and R⁴⁰⁰, when present, is selected from hydrogen, C1-C3 alkyl. Cl -C3 monohaloalkyl, and €1-C3 polyhaloalkyl,

Also disclosed are filtration membranes comprising a polymer comprising a structure represented by a formula:

R^a‘\ R^2b

\>^v

βά ,R3=

Λ

ⁿ^«3b

wherein each. Ζ is independently selected from hydrogee and R ; wherein η is an integer selected from 1, 2, and 3; wherein ρ is independently 0, 0.5, or 1; wherein q is independently 0, 0.5, or 1; wherein, for each χ, ρ 4 q~ I ; wherein each ofR‘*„ R'*, R^Sc, and R^hi is independently selected from hydrogen, halogen, -CN, -S.R^2e, -OR"\ -NR^{: ;il}R"^3b,

-NR“^aR^22bH\ ~SOjR²\ -(C-OiR²⁴, and C1-C3 alkyl substituted with 0,1, 2, or 3 groups selected from halogen, -CN, -SR²*, -OR", -NR.^22:lR^22b, -SQsR²³, and-~<C><))R²⁴;

wherein, each of R^2s and R^2b is independently selected from hydrogen, halogen, -CN,

-SR³⁰, -OR³¹, ~NR^32aR³²\ -NR³²*R^325,fT, ~S0₂Rfo ~~(0-O)R³⁴, and C1-C3 alkyl substituted with 0, 1, 2, or 3 groups selected from halogen, -CN, - SR^;,U, -OR³*,

-NR²²*R^52b, -SOdO³, and -(OOJR³⁴; wherein each of R^3s, R³\ and R^S£ is independently selected from hydrogen, halogen, -CN, -SR.⁴⁰, -OR⁴⁵, -NR⁴*^aR^42b, -NR^42sR^42bH",

■SOjR⁴⁵, and -<C==0)R*‘; wherein each ofR'*', R^4f, R“^a, R'“'^c, R:^H’, R”, R^taa, R:^!at\ R

>44

20

>22a

illh

>3(3 r) .>: f> 32¾ T>32h

j-W

R⁴*, R⁴²*, and R'^uo, when present, is independently selected from hydrogen, CS.-C3 alkyl, C1-C3 monohaloaikyl, and .CI-C3 polyhaloalkyi; wherein each ofR'“’ and R²⁴, when present, is independently selected from-0\-OR^i;, C1-C3 alkyl, Cl-C3 monohaloaikyl, C1-C3 polyhaloalkyi., and - NR^R²⁶⁰; wherein each of R^aS, R^abs, and R^A*, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloaikyl, and Cl-C3 ,42b

polyhaloalkyi; wherein each of R³³ and R³⁴, when present, is independently selected from.

■-¹0‘,~-OR³⁵, C1-C3 alkyl, C1-C3 monohaloaikyl, C1-C3 polyhaloalkyi, and -NR^R³⁰⁶;

wherein each of R³\ R^M>3, and R^36b, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloaikyl, and C1-C3 polyhaloalkyi; wherein each of R⁴³ and R⁴⁴, when present, is independently selected from-O',-OR⁴³, C1-C3 alkyl, C1-C3 monohaloaikyl, CI-C3 polyhaloalkyi, and -NR'^kaR^4fo; wherein each of R⁴\ R⁴⁶*, and R⁴⁶*, when present, is selected from hydrogen, Cl-C3 alkyl, Cl-C3 monohaloaikyl, and C1-C3 polyhaloalkyi: and wherein at least one Ζ is a structure represented by a formula :

, and

wherein at least one of R^;i, R"⁰, R³*, R³⁰, and is not hydrogen

Also disclosed are polymers formed by polymerizing a compound having a structure represented by a formula;

s 10 15 20 '75 wherein η is selected from 1

and 3; wherein each of R.^;l R^U:. R^ic, and R;^U! is independently selected from hydrogen, halogen, -CN, -SRⁱ⁰, -OR*¹, “NR'^:UaR^a'^r:a,

-SOjR"', -{0=0)R²⁴, and C1-C3 alkyl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, -SR²⁰, -OR²ⁱ, -NR^22aR^22,>, -S0₂R^r!, and -lX>0)R²⁴;

wherein each of R^2a and R^ii? is independently selected from hydrogen, halogen, -CN,

-SR⁵⁰, -OR³¹, -NR^32aR^m« “NR^33aR³³*H\ -S0₂R³³, -(C^O)R⁵⁴, and C1-C3 alkyl substituted with. 0,1,2, or 3 groups selected from, halogen, -CN, -SR^-’⁰, “OR³’ ,

-N^rR^35BR:'^,2a-S0₂R⁵⁵, and ~~(00).R'’⁴; wherein each of R^,,!, R^Jb, and R’^a is independently selected from hydrogen, halogen. “CN, “SR⁴⁰, -OR⁴¹, “NR^4ailR⁴'^:’’_s -NR^42kR^4,!0H’\ “SOjR⁴", and-(OOJR⁴*; wherein at least one of R'^:S, R²⁰, R^as, R'^b, and R‘’^c is not.

hydrogen; wherein each of R²⁰, R²’, R^m,R"\R³⁰, R^4t, R^32a, R³²\R^m,R⁴⁵,R⁴²\ and R^42h.

when present, is independently selected, from hydrogen, CIO alkyl, CIO monohaloalkyl, and CIO polyhaloalkyl; wherein each of R^4-5 and R⁴⁴, when present, is independently selected from-O',-OR³⁵, CIO alkyl, CIO monohaloalkyl, C1-C3 polyhaloalkyl, and-NR"^6aR^?'^(w; wherein each of R²\ R^20a, and R^46b, when present, is independently selected from hydrogen, CIO alkyl, CIO .monohaloalkyl, and C1-C3 polyhaloalkyl; wherein each of R” and R'⁵⁴, when present, is independently selected from

-O',-OR³⁵, CIO alkyl, CIO monohaloalkyl, CIO polyhaloalkyl, and -NR^34aR³*^b;

wherein each o.fR’^>5, R^H,S, and R'^f'\ when present, is independently selected from hydrogen, Cl*C3 alkyl, CI-C3 monohaloalkyl, and C1*C3 polyhaloalkyl; wherein each of R⁴'¹ and R⁴⁴, when present, is independently selected from-O',-OR⁴⁵, CIO alkyl, CIO monohaloalkyl, CI-C3 polyhaloalkyl, and -NR^4tMR^4(>u; and. wherein each of R."*⁵, R⁴⁰*, and R⁴**, when present, is selected from hydrogen, CIO alkyl, CIO monohaloalkyl, and Cl C3 polyhaloaUtyl.

Also disclosed are polymers comprising a structure represented fay a formula;

wherein each 2 is independently selected from hydrogen and

ril^*

wherein η is an integer selected from 1,2, and 3; wherein ρ Is independently 0,0.5, or i; wherein q Is independently 0, 0,5, or i ; wherein, for each χ, ρ 4- q ≈ I ; wherein each ofR'\ R^!f>, R'*, and R^!d is independently selected from hydrogen, halogen, -CN, -SR⁵⁰, -OR"^:1, -NR'^'TO⁴*,.

-NR^??3R^2?-^l,H\ “S0₂R^b, -(CO)R²⁴, and CI-C3 alkyl substituted with 0,1, 2, or 3 groups selected front halogen, -CM, -SR²®, -OR³ⁱ, -NE^BaR^m, -SO?R²⁵, and-<C=0)R²⁴;

wherein each ofR"¹ and is independently selected from hy drogen, halogen, -CN,

-SR³⁰, “OR^3!, -NR'^52ilR^32&, -NR⁵²⁸R^mH'^!', -SO^R⁵⁵, “(C-O)R³⁴, and C1-C3 alkyl substituted with 0, 1, 2, or 3 groups selected from halogen, -CN, -SR;’⁰. -OR^ji,

-NfR^32aR^32b, ™S0₂R³\ and -(C^::0)R³⁴; wherein each ofR³⁸, R^Jb, and R³' is independently selected from hydrogen, halogen, -CM, -SR⁴⁰, ~OR^4!, ™NR^4BR^4B ™NR^4BR^42bf-f,

-SCKR⁴³, and -(GOfR⁴⁴; wherein each ofR²⁰, R^3!, R²²⁸,R^u\R³⁰, R^3!, R^52a, R⁵²\ R⁴⁰, R⁴ⁱ, R^42a, and R*^ab, when present, is independently selected from hydrogen, Cl-C.3 alkyl, CI-C3 monohaloalkyl, and CI-C3 polyhaloalkyl; wherein each of R^B and R'⁴, when present, is independently selected from -O',-OR"’, CI-C3 alkyl, C1-C3 monohaloalkyl, CI-C3 polyhaloalkyl, and -NR^2<,aR²*^b: wherein each ofR"³, R"'^s, and R^Bl>, when present, is independently selected from hydrogen, CI-C3 alkyl, C1-C3 monohaloalkyl, andCl-C3 polyhaloalkyl; wherein each of R" and R'⁴, when present, is independently selected from

-O',-OR³’, CI-C3 alkyl, CI-C3 monohaloalkyl, C1-C3 polyhaloalkyl, and -NR^R:’⁰®; wherein each of R"’\ R:’⁶®, and when present, is independently selected from hydrogen, C1 -€3 alkyl, € 1-C3 monohaloalkyl, and CI-C3 polyhaloalkyl; wherein each of R⁴'⁵ and R⁴⁴, when present, is independently selected from -O', -OR⁴⁵, C1-C3 alkyl. Cl -C3 monohaloalkyl, Cl-C3 polyhaloalkyl, and “NR^4feR^4fi0; wherein each ofR⁴⁵, R^4fia, and R⁴'^!\ when present, is selected from: hydrogen, C1-C3 alkyl, C1-C3 monohaioaikyl, and CI-C3 polyhaloaikyl; and wherein at least one Ζ is a structure represented by a formula:

_R2a_R2b

VlV^R3c

\ nhpsfc

and

wherein at least one ofR**, R^2b, R^, and R:^>e is not hydrogen.

Also disclosed are methods of making filtration membranes.

Also disclosed are methods of filtering water through membranes.

While aspects of the present invention can be described and claimed in a particular statutory' class, such as the system statutory class, this is for convenience only and one of skill in the art will understand that each aspect of the present in vention can be

10 described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim: does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred, in any respect. Th is holds for any 1S possible non-express basts for interpretation, including matters of logic with respect to arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

The accompanying figures, which are incorporated in and constitute a part of this 20 specification, illustrate several aspects and together with the description serve to explain the principles of the invention,

FIG, I shows representative data pertaining to the effect of being soaked in bleach containing 250 ppm free chlorine for 2 days on the physical appearance of n-Pani membranes compared to Pani and PSf membranes.

FIG, 2 shows representative data pertaining to the contact angle of n-PANi and PANi membranes before and after being soaked in 250 ppm free chlorine.

FIG. 3 shows representative data pertaining to the effect of chlorine on the benzenoid and quinoid groups in polyaniline membranes as observed by FT-IR analysis.

FIG. 4 shows representative data pertaining to the effect of chlorine on the benzenoid and quinoid groups in polyamline membranes as observed by IJV-Vis analysts,

FIG. S shows representati ve data pertaining to the effect of chlorine on the benzenoid and quinoid groups in polyamline membranes as observed by Nuclear Magnetic Resonance (NMR) analysis.

FIG. 6 shows images from bacterial adhesion tests that indicate that «~Pam membranes are more resistant to fouling than Pani membranes.

FIG. 7 shows flux decline and recovery for membranes fouled by 1.5 g/L BSA solution before being flushed with DI water.

FIG. 8 has 12 panels (a-1), depicting SEM images. Panel (a) depicts a PANi membrane and and Panel (b) depicts a n-PANi membrane surface at 3,000* magnification;

Panel (e) depicts a n-PANi membrane surface at 100,000* magnification and Panel (d) depicts its black-white picture after conversion using image J software. Panels (℮)-(1ΐ) depict cross-sectional images of (℮) pristine PANi membrane, (f) PANi membrane after chlorine exposure, (g) pristine n-PANi membrane and (h) n-PANi membrane after chlorine exposure at 600* magnification. Panels (i)-(l) depict surface images of (i) pristine 'PANI membrane,

(j) PANi membrane after chlorine exposure, (k) pristine n-PANi membrane and (I) n-PANi membrane after chlorine exposure at 600* magnification.

Addi tional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or can be learned by practice of the invention. The advantages of the in vention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and arc not restrictive of the invention, as claimed.

The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein.

Before the present compounds, compositions, articles, systems, devices, and/or methods arc disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such may, of course, vary, it is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, example methods and materials are now described.

All publications mentioned .herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. Further, the dates of publication provided herein can be different from the actual publication dates, which can require independent confirmation.

As used herein, nomenclature for compounds, including organic compounds, can be given using common names, RJPAC, RJBMB, or CAS recommendations for nomenclature. When one or more stereochemical features are present, Cahn-lngold-Prelog rides for stereochemistry can be employed to designate stereochemical priority, EIZ specification, and the like. One of skill in the art can readily ascertain the structure of a compound if gi ven a name, either by sy stemic reduction of the compound structure using naming con ventions, or by commercially available software, such as CHEMDRA W^5M(Cambridgesoft Corporation, U.S.A.).

As used in the specification and die appended claims, the singular forms “a,” “an” and “the’⁷ include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a functional group,” “an alkyl,” or “a residue” includes mixtures of two or more suck functional groups, alkyls, or residues, and the like.

Ranges can he expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, a further aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. It will be further understood that the endpoints of each of the ranges are signi ficant both in relation to the other endpoint, and independently of the other endpoint, if is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. If is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11,12, 13, and 14 are also disclosed.

References in the specification and concluding claims to parts by weight of a particular element or component m a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Υ, X and Υ are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

A weight, percent (wt. %) of a component, unless speci fically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

As used herein, the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

A residue of a chemical species, as used in the specification and concluding claims, refers to the moiety that is the resulting product, of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the moiety is actually obtained from the chemical species. Thus, an ethylene glycol residue in a polyester refers to one or more -OCMjCHjO- units in the polyester, regardless of whether ethylene glycol was used to prepare the polyester. Similarly, a sebaeic acid residue in a polyester refers to one or more -CCXCBekCO- moieties in the polyester, regardless of whether the residue is obtained by reacting sebacic acid or an ester thereof to obtain the polyester.

As used herein, the term “polymer' refers to a relatively high molecular weight organic compound, natural or synthetic, whose structure can be represented by a repeated small unit, the monomer (e.g., polyethylene, rubber, cellulose). Synthetic polymers are typically formed by addition or condensation polymerization of monomers.

to As used herein, the term “copolymer’ refers to a. polymer formed from two or more different repeating units (monomer residues). By way of example and without limitation, a copolymer can be an alternating copolymer, a random copolymer, a block copolymer, or a graft copolymer, it is also contemplated that, in certain aspects, various block segments of a block copolymer can themselves comprise copolymers.

IS As used herein, the term “oligomer” refers to a relatively low molecular weight polymer in which the number of r epeating units is between two and ten, for example, from two to eight, from two to six, or form two to four. In one aspect a collection of oligomers can have an average number of repeating units of from about two to about ten, for example, from about two to about eight, from about two to about six, or form about two to about

20 four.

As used herein, the term “molecular weight” (MW) refers to the mass of one molecule of that substance, relative to the unified atomic mass unit it (equal to 1 /12 the mass of one atom of carbon-12 ),

As used herein, the term “number average molecular weight” (M.,) refers to the common, mean, average of the molecular weights of the indi vidual polymers. M_B can be determined by measuring the molecular weight of η polymer molecules, summing the weights, and dividing by η. Μ,, is calculated by:

wherein Nj is the number of molecules of molecular weight Μ;, The number average molecular weight of a polymer can be determined by gel permeation chromatography, viscometry (Mark-Houwink equation), light scattering, analytical iiltracentriiitgation, vapor pressure osmometry, end-group titration, and eoiligative properties.

As used herein, the term ‘"weight average molecular weight” (M_w) refers to an alternative measure of the molecular weight of a polymer. M_w is calculated by:

wherein N_; is the number of molecules of molecular weight M„ Intuitively, if the weight average molecular weight is w, and a random monomer is selected, then the polymer it belongs to will have a weight of w, on average. The weight average molecular weight can be determined by light scattering, small angle neutron scattering (SANS), X-ray scattering, and sedimentation velocity.

As used herein, the terms “polydispersity ’ and “polydispersity index” refer to the ratio of the weight average to the number average

As used herein, the terms “flash welding⁵’ and “flash weld” refer to applying a pulse of light to an absorbing material. Flash welding can provide enhanced photothermal phenomena when performed on polymeric nanofibers, in certain aspects, the material rapidly converts tire light to heat and then undergoes a transformation, such as melting, it. is understood that, in certain aspects, chemical reactions can take place in the material as a consequence of flash welding. Techniques for performing flash welding are described in U.S. Patent No, 7,850,798 (“Flash welding of conducting polymers nanofibers”), issued December 14, 2010, to J, Huang and R. Β. Kaner.

Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art For example, the starling materials and reagents used in preparing tire disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co,, (Milwaukee, Wis.), Acres Organics (Morris Plains, N.J.), Fisher Scientific (Pittsburgh, Pa.), or Sigma (St. Louis, Mo.) or are prepared by methods known to those skilled in the art following procedures set forth in references such as Fieser and Fieser’s Reagents for Organic Synthesis, Volumes 1-17 (John Wiley and Sons, 1.991);

Rodd's Chemistry of Carbon Compounds, Volumes 1 -5 and Supplemental volumes (Elsevier Science Publishers, 1989); Organic Reactions, Volumes 1-40 (John Wiley and Sons, 1.991 ); March’s Advanced Organic Chemistry, (John Wiley and Sons, 4th Edition);

and Laredo s Comprehensive Organic Transformations (V'CH Publishers Inc,, 1989),

Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order.

Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise speci fically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

Disclosed are the components to he used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that, when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described .herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that arc possible unless specifically indicated to the contrary. Thus, if a class of molecules A, Β, and C are disclosed as well as a class of molecules D, Ε, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A~B, A-.F, B-D, B~E, B~F, C-D, C-E, and OF are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of Α-Ε, B-F, and C-E would be considered disclosed. This concept, applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the methods of the invention.

S It is understood that the compositions disclosed herein have certain functions.

Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of struc tures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.

ΐο Β, Filtration Membranes

In one aspect, the membranes of the invention relates to a filtration membrane comprising a polymer formed by polymerizing a compound having a structure represented by a formula:

„ ? Η T_R” pis c>3<;

Η f R^d J^R^2a'

R¹"

15 wherein η is selected from 1,2, and 3; wherein each of R , R , R , and R is independently selected from hydrogen, halogen,-CN, -SR⁴⁰, -OR'¹¹, -NR~~^aR“^B,

-NR^R^fT, ~SOjR²‘\ -(C^:::Q)Rⁱ⁴, and C1-C3 alkyl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, “SR"'⁰, -OR^J:, -NR"^:'^;!lR'^{; :h}, -SOjR⁴⁴, and-(C=0)R'^:4; wherein each of R~^J and R^25> is independently selected from hydrogen, halogen, -CN,

20 -SR³⁰, -OR^?\ -NR⁵²⁰R^?3:b, -NRⁱ²*R^32bfi'^>, -SOjRA -(Ο0)ΐΑ, and CI-C3 alkyl substituted with 0, 1, 2, or 3 groups selected from halogen, -CN, -SR’¹’, -OR’¹,

-- SCTRA and ■-(0≈0)Β^; wherein each of R^Ki, R^>b, andR'³ is independently selected from hydrogen, halogen, -CN, -SR⁴⁰, -OR⁴*, -NR^{4 ;a}R^4:b, -NR^43aR⁴"^:bFT,

-SO?R⁴\ and-(0^:::0)R^{15 44*;} wherein at least one of R”'¹, R^4b, R'⁰, RA and is not hydrogen; wherein each ofR²⁰, R^Ji, R^22a, R^22b, R^M, R^:n, R^Kft, R^52b, R⁴% K⁴\R^42a, and R^42b, when present, is independently selected from hydrogen, C1-C3 alkyl, Cl -C3 monohaloalkyl, and C1-C3 polyhaloalkyl; wherein each of R“"' and R^a4, when present, is independently selected from -O',-OR~% C1-C3 alkyl, C1.-C3 monohaloalkyl, C1-C3 polyhaloalkyl, and wherein each of R.²⁵, R^J<‘\ and R^J,b, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl; wherein each of R'^v and R'^t4, when present, is independently selected from

-O',-OR³⁵, CI-C3 alkyl, CI-C3 monohaloalkyl, C1-C3 polyhaloalkyl and -NR^3feR^36S>;

wherein each of R”, R^>fca, and R'”^w, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl; wherein each of R⁴‘ and R⁴⁴, when present, is independently selected from -0”,-OR⁴⁵, C1-C3 alkyl, C1-C3 monohaloalkyl, C1-C3 polyhaloalkyl, and -NR'^i<>aR^fk*; and wherein each of R⁴‘\ R⁴⁶*, and R4^<9>, when present, is selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and Cl-C3 polyhaloalkyl.

In one aspect, the invention relates to filtration membranes comprising a polymer comprising a structure represented by a formula:

Μ '<* / R- R^1d /

\ nfooSb

wherein each 2 is independently selected from hydrogen and R³* ; wherein η is an

integer selected from 1, 2, and 3; wherein ρ is independently 0, 0.5, or 1; wherein q is independently 0,0,5, or 1; wherein, for each χ, ρ + q ≈ 1 ; wherein each of R^Sii, R^,fe, R^u', and R^w is independently selected from hydrogen, halogen, -CN, -SR²⁰, -OR'^a, -NR^R"¹'*

-NR^??aR^22l>H\ -SQ₂R^b, -fC-0)R^;!4, and C1-C3 alkyl substituted with 0,1, 2, or 3 groups selected from halogen, -CN, -SR²⁰ -OR³*, -NR^R"²⁰, - SCCR'l and -(C=0)R²⁴;

wherein each of R²* and R^ih is independently selected from hy drogen, halogen, -CN,

-SR³⁰, -OR³ⁱ,-NR³²⁸R^32b, -NR³²*R³*H',™SQ?R⁵³, -(0===0)¾³⁴. and C1-C3 alkyl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, -SR⁴⁰, -OR⁵*,

-NR/'^R^, - SOiR'y and-(C=<3)R⁴'*; wherein each of R^JS, R^,b, andR'^v is independently selected from hydrogen, halogen, -CN, -SR⁴⁰, -OR^4{,-NR^42aR^42b, -NR⁴²⁸R^42hH\

-S0₂R⁴⁵, and -(OO)R⁴⁴; wherein each ofR²⁰, R²*, R“\ Rⁿ\R³⁰, R^3!, R³²\ R^32b, R⁴⁰, R⁴¹, R⁴²\ and R⁴²¹", when present, is independently selected from hydrogen, CI-C3 alkyl Ci~C3 monohaloaikyl and C1-C3 polyhaloaikyl; wherein each ofR^4;’ and R~\ when present, is independently selected from --O',-OR'^:\ CI-C3 alkyl, C1-C3 monohaloaikyl, C1-C3 polyha.ioa.ikyl, and “NR^R²⁶⁶; wherein each of R⁴\ R^4{Ki, and R⁴'*, when present, is independently selected from hydrogen, CI-C3 alkyl, CI-C3 monohaloaikyl, and C1-C3 polyhaloaikyl; wherein each of R” and Rf⁴, when present, is independently selected from

-0;-0R^3S, CI-C3 alkyl, C1-C3 monohaloaikyl, C1-C3 polyhaloaikyl, and -NR^R³®’;

wherein each ofR:’⁵, R and R'^, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloaikyl and C1-C3 polyhaloaikyl; wherein each of R⁴' and R⁴⁴, when present, is independently selected from -0*, -OR⁴*, C1-C3 alkyl, C1-C3 monohaloaikyl C1-C3 polyhaloaikyl and-NR^R⁴⁶⁰; wherein each of R^4S, R⁴⁶³, and R^4<’^f>, when present, is selected from hydrogen, Cl -03 alkyl, Cl -03 monohaloaikyl, and C.1-C3 polyhaloaikyl: and wherein at least one Ζ is a structure represented by a formula :

R^s\ R^a w_R3c

R and

wherein at least one of R'C R^2t\ R^JS, R'\ and R'" is not hydrogen,

hi a further aspect, the filtration membrane is selected from an nltrafiitration membrane, a nanofihration membrane, a reverse osmosis membrane, a forward osmosis membrane, and a pressure retarded osmosis membrane without thin film coating. In a still further aspect, the filtration membrane is selected from an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane and a forward osmosis membrane.

In yet a further aspect, the filtration membrane is selected from an ultrafiltration membrane and a nanofihration membrane. In an even further aspect, the filtration membrane is an uitrafiitrafion membrane. In a still further aspect, the filtration membrane is a nanofihration membrane.

In a further aspect, the filtration membrane further comprises a thin film polymerized onto a surface of the membrane, thereby providing an osmosis membrane. In a still further aspect, the osmosis membrane is selected from a reverse osmosis membrane and a forward osmosis membrane. In yet a further aspect, the osmosis membrane is a reverse osmosis membrane. 1« an even further aspect, the osmosis membrane is a forward osmosis membrane.

L Polymers

In one aspect, the invention relates to polymers useful as components of filtration membranes. In various aspects, the polymers can improve properties of the membrane. For example, the polymers may improve the chlorine-resistance of the membrane and/or the hydrophilicity of the membrane.

In a further aspect, the polymer is present in an amount from about 0.1 wt% to about 40 wt%. In a still further aspect, the polymer is present in an amount from about 0.1 wt% to about 35 \vt%. In yet a further aspect, the polymer is present in an amount from about 0.1 wt% to about 30 wt%, in an even further aspect, the polymer is present in an amount from about 0,1 wt% to about 25 wt%. In a still further aspect, the polymer is present in an amount from about 0.1 wt% to about 20 wt%. In yet a further aspect, the polymer is present in an amount from about 0.1 \vt% to about 15 \vt%. in an even further aspect, the polymer is present in an amount from about 15 \vt% to about 40 wt%. In a still further aspect, the polymer is present in an amount from about .15 wt% to about 40 wt%. In yet a further aspect, the polymer is present in an amount from about 20 wt% to about 40 wt%. In an even further aspect, the polymer is present in an amount from about 25 wt% to about 40 wf%. In. a. still further aspect, the polymer is present in an amount from about 30 wl% to about 40 wt%.

In a further aspect, the membrane further comprises a second polymer. In a still farther aspect, the second polymer is selected from polysulfone, polyurethane, cellulose acetate, sulfonated polysulfone, polyethersulfone, stilfonated polyethersulfone, polyamlinc, polyaniline co-polymers, polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyperfiuoroalkyl vinyl ether, polyhexafluoropFopylene, cellulose acetate, polyurethane, or a mixture thereof In yet a further aspect, the second polymer is polysulfone.

It is contemplated that each disclosed deri vative can be optionally further substituted. It is also contemplated that any one or more derivative can be optionally omitted from: the invention. It is understood that a disclosed compound can be provided by the disclosed methods. It is also understood that the disclosed compounds can be employed in the disclosed methods of using.

wherein η is selected from 1,2, and 3; wherein each of R^ia, Rⁱ⁰, R*\ and R^Ulis independently selected from hydrogen, halogen, -ON, -SR⁵" -OR^: \ -NR^R"",

-NR^22aR^22bH⁴, -S0₃R^;B, -<C=0)R^J4, and C1-C3 alkyl substituted with 0,1,2, or 3 groups selected from halogen, ™CN, -SR²⁰, -OR²⁵,-NR^22aR^22b, -S0₂R²³, and ~{0=0)R.²⁴;

wherein each ofR²* and R^2b is independently selected from hydrogen, halogen, -€N,

-SR⁵⁰, -OR³¹, ~NR^32aR^m, ~NR³²*R^32bH\ -SCKR³³, ~((>0)R⁵⁴, and C1-C3 alkyl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, - SR'°, -OR³¹,

-NR^33sR^m, -SG₂R^B, and -(00).R³⁴; wherein each of R^3a, R^Sb, and R³° is independently selected from hydrogen, halogen, -CN, -SR⁴⁰, -OR⁴¹, -NR^42aR⁴²\ -NR^42aR^42bH%

-S0₂R⁴\ and -(C=0)R⁴⁴; wherein at least one of R'^:\ R^2b, R^as, R^!\ and R^JC is not

when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaioalkyl, andCi-C3 poiyhaloalkyl; wherein each of R^aJ and R'^:"\ when present, is independently selected from -O',-OR³⁵, C1-C3 alkyl, C1-C3 monohaioalkyl, CI-C3 poiyhaloalkyl, and- NR"^6bR^2oi>; wherein each o£R²\ R^20s, and R^a<>b, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaioalkyl, and C1-C3 poiyhaloalkyl: wherein each of R“ and R*⁴, when present, is independently selected from.

-O’, -OR³⁵, C1-C3 alkyl, C1-C3 monohaioalkyl C1-C3 poiyhaloalkyl, and -NR^3feR³⁰⁰;

wherein each of R.^a5, R^M,\ and R'^h!\ when present, is independently selected from hydrogen, CI-C3 alkyl, C1-C3 monohaioalkyl, andCl-C'3 poiyhaloalkyl; wherein each ofR⁴⁵ and R⁴⁴, when present, is independently selected from -O’, -OR⁴⁵, Cl -C3 alkyl. Cl -C3 monohaioalkyl, C1-C3 poiyhaloalkyl, and -NR^4wR^46s; and wherein each o.fR*⁵, R⁴“l and a. Structure

In one aspect, the invention relates to polymers formed, by polymerizing a compound having a structure represented by a. formula;

R.⁴⁶*, when present is selected from hydrogen, C1-C3 aikyi, C1-C3 monohaloalkyl, and €1-C3 pofyhaloalkyl.

In a further aspect, the polymer comprises at least one residue of a compound having a structure represented by a formula:

present in an amount of at least 0.1 wt%. In a still further aspect, the at least one residue of a compound is present in art amount of at least 0.5 wt%. In yet a further aspect, the at least one residue of a compound is present in an amount of at least 1 wt%. In an even further aspect, the at least one residue of a compound is present in an amount of at least 5 wt%. In a Η) still further aspect, the at least one residue of a compound is present in an amount of at least 10 wt%. la yet a further aspect, the at least one residue of a compound is present in an.

amount of at. least .15 wt%. In an even further aspect, the at least one residue of a compound is present in an amount of at least 25 wt%. In a still further aspect, the at feast one residue of a compound is present man amount of at least 50 wt%. In yet a further aspect, the at

15 least one residue of a compound is presen t in an amount of at least 75 wt%.

In one aspect, the invention relates to polymers comprising a structure represented by a formula:

20 integer selected from 1, 2, and 3; wherein ρ is independently 0, 0.5, or 1; wherein q is independently 0, 0,5, or i ; wherein, for each χ, ρ 4- q ≈ I : wherein each ofR'\ R^!f>, R'*, and is independently selected from hydrogen, halogen, -CN, -SR²⁰, -OR²’, - NR²~^aR^22!\

-- SOjR³', -(OO)R²⁴, and C1-C3 alkyl substituted with 0, .5, 2, or 3 groups selected from halogen, -CN, -SR¹⁰, -OR^-NR^mR^m, -SCKR²², and-<C>0)R²⁴;

wherein each of R~" and R^25> is independently selected from hydrogen, halogen, -CN,

5 -SR²⁰, ~OR^Si, -NR^22aR^S2b, ~NR^22aR^J2*H’_f -SCfrR²². -(OO)R²⁴, and C1-C3 alkyl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, - SR'¹⁰, -OR'^>{,

-NR/'^;aR^j2\ - SO^R²', and -(O=0)R'~; wherein each of R^JS, R²\ and R-* is independently selected from hydrogen, halogen, -CN. -SR⁴⁰, -OR⁴*, -NR^42i!R^42b, -NR⁴²⁸R^42bH'\

-SO?R⁴\ and -(C-O)R⁴*; wherein each of R²⁰, R²*, R^22a, R²²\ R³⁰, R^Jf, R^32a, R^m, R‘^w,

It) R^4t, R⁴²⁵, and R'^lib, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl., and Ci-C3 polyhaloalkyl; wherein each ofR" and R²⁴ when present, is independently selected from-0 ,-OR⁴², C1-C3 alkyl, CI-C3 monohaloalkyl, C1-C3 polyhaloalkyl, and -NR^2f,3R²⁽*; wherein each of R^;R^2ta, and R²"⁰, when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, atid€l-C3

S S polyhaloalkyl; wherein each of R^v' and R^>4, when present, is independently selected from

-O", -OR⁵⁵, C1-C3 alkyl, C1-C3 monohaloalkyl, C1-C3 polyhaloalkyl, and ~NR**R^3Sb;

wherein each of R²‘\ R‘ⁿ"*, and R’⁰⁰, when present, is independently selected from hydrogen, CI-C3 alky!, C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl; wherein each of R⁴'¹ and R⁴⁴, when present, is independently selected from -G, -OR⁴', C1 ~C3 alkyl, C1-C3

20 monohaloalkyl, C1-C3 polyhaloalkyl, and -NR⁴"¹!?⁴™'; wherein each of R⁴\ R^4l,;\ and R^4t,t\ when present, is selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl; and wherein at least one Ζ is a structure represented by a formula:

wherein at least one of R"^a, R"⁰, R'\ R^3v, and R'^<v is not hydrogen.

In a further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

Η R'^5c

Η I „R^3b

hL ^Νν/ V- , ,,

γ; -fo- \xfn R³³

^x7 VV ∩

AR²³

. , //_NR^2a R²³

_H" -γ

In a still further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula selected from:

Η R'^>c ,,

j Η ,R^3b

^ w η^K

H' Τ

Η

v κ

Η Η

Η

1

Η Η

j Η f ,Η

it A^H

_R3a_R20

"H

η "" γ

ami Η

In a further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula;

3133

R R* „

Η i ,R³⁵

^1R3a

τ

R^1f-

/Υ

Η Η

'R¹⁰

wherein each of.R.'^>a, R'% and. R'" is independently selected from hydrogen, halogen,-CN,

-SR⁴⁰, -OR⁴¹, “NR^43aR^42b, “NR^4IaR⁴³*H'\ -SOjR⁴³, and “(C-O)R⁴⁴; and wherein at 10 least one of R'^a, R’^fi, and R^4V is not hydrogen.

lit a still further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

R^J

»13

] η t-,^R

.A ,ν./vk

rsr^T

yV π

Η Η

_sb

h^x

R

1c

wherein each of R'^>a and R^a is hydrogen and is selected from halogen, -CN, -SR⁴⁰, 1« yet a further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

wherein each of R'" and R:^>5> is hydrogen and R:^>s is selected from halogen, -CM, -SH,

5 -OH, -NHs, -ΝΗ/, ~S0_;0\ -SOjO'H, -(00)0; and -(Ο0)0Η.

In an even tardier aspect, the invention relates to polymers formed by

poly merizing a compound having a structure represented by a formula:

wherein each of R^M and R'^>h is hydrogen and R'’* is selected from -SH, -OH,

SO -NH.f, -S( >:■()', “SOjOH,~<COyO\ and -(℮Ο)0Η.

In a still further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

wherein each of R^M and R'^A is hydrogen and R^:>t is selected from -SH, -OH, -Ν¾

1S -SlfoOH, and -(ΟΟ)0Η.

In a further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

R^1s Η

Ri "V ^/n'H X R²ⁱⁱ R^ab

Η 'f R^;"

R^1b

wherein each of R^2il and R^Jtt is independently selected from hydrogen, halogen, ~~CN,

-SR⁵⁰, -OR³¹, ~NR^32aR³²⁵\ ~NR³²*R³²ⁱlBr, -SCKR³³, ~(C==0)R⁵⁴, and C1-C3 alkyl substituted with 0,1,2, or 3 groups selected .from halogen, -C/M, -SR'^!!), -OR^;(i,

-NR^{3 J,1}R'^,"'^y, - SOaR^3>, and -f C=0)R^J"; and wherein at least one of 1Χ and R"^4> is not hydrogen.

In a still further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

R^;? Η

R .X X X "X'- /η Η

X R²⁸ R^2b

Η

R^!ic

10 wherein R^* is hydrogen and R is selected from halogen, -CM, -SR , -OR,:η

-NR^32sR^m, -NR^:!2:!R'^i2bH2-SCMR³³, ~(O0)R³\ and C1-C3 alkyl substituted with 0. i, 2 or 3 groups selected from halogen, -CN, -SR'⁰, -OR'^f, -NR^'^R”²⁵’, - SO^R⁴'*, and

-(D=0)R34

In yet a further aspect, the invention relates to polymers formed by polymerizing i.5 a compound having a structure represented by a formula:

Rlb pia I Η v- Η Η Η

Η Y' 'fX . jX R^2b

R^1c

wherein R²³ is hydrogen and R^3b is selected from halogen, -CM, - SR'⁰, -OR'⁵*,

1« an even further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

Rib χ χ y^h1 ...... R^;* R^Jb ' W'' ^fn^H γ "R^1<| R^1s Η

R^1c

wherein 87“ is hydrogen and R"^fc is selected from .halogen, · :r -sh, -oh, -nh₃.

5 -Ν¾ \ -SOjO', -SOjOH,-iC-0)0’, and -(0-0)0Η.

In a still further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

R‘^& Η

R\_]f V Wn^H A ,. N y v< Η foH R^2b

" R^ia

R^1c

wherein Rf* is hydrogen and R'* is selected from-SH, -OH, -NHj, -Ml.f, -SCMT,

10 -SOjOH, -(00)0. and -(Ο0)0Η.

In yet a further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

RH" 'Y" "'R^1d jf 1 .wn R^ls i^H 'LH -^Nf_x>' R^2a R^2b yVrΗ

RU-

wherein R~^a is hydrogen and R'^J is selected from-SH, -OH, -NH₃, -SOjOH, and

iS -(Ο=0)0Η.

In an even further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

R^1s Η

Ri "V ^/n'H R^ab

Η 'f R^;"

-(℮=-0)Κ³⁴.

10 In yet a further aspect, tlie invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

R^,a Η

ΗVvV« A .^R^{2a R2b} r R' Η Η

RlC

wherein R³* is hydrogen and is methyl substituted with 0, 1,2, or 3 groups selected from halogen, ~CN, ~SR³⁰, -OR^5!, -~NR^S2aR^3Jb, -~S0₂R³³, and ~-((>0)R’⁴

{S In an even further aspect, the invention relates to polymers formed by polymerizing a compound having a structure represented by a formula:

RllI_ M j ^ ^/Π Η r2s_Rab Η 1η

H'"γ R^;'

R^1C

wherein R³³is .hydrogen and R^Jb is CIO alky! substituted with 0,1, or 2 groups selected from halogen, -CN, -SR™, ~<)R⁵\-~NR^32aR³²\ -SO,R³l and ™CO=0}R^M

In a still. further aspect, die Invention relates to polymers formed by polymerizing a compound having a structure represented by a formula;

wherein R~* is hydrogen and R‘ is C.I-C3 alkyl substituted with 0 or 1 group selected from halogen, ~~CN, -SR⁵⁰, -OR³¹, 'NR³'*R³²\ -SOjR⁵⁵, and ~((>=0)R^M

In yet a further aspect, the invention relates to polymers formed by polymerizing 10 a compound having a structure represented by a formula:

R'^e π

ΑΛ^Η Η

Η

R^1c

wherein. R³³ is hydrogen and R™ is unsubstituted C.I-C3 alkyl.

In a further aspect, the polymers of the invention further comprise a counterion Examples of counterions include, but are not limited to, chloride, fluoride, bromide,

1S carbonate, hydrogen carbonate, phosphate, acetate, formate, oxalate, cyanide, sulfate, perchlorate, and nitrate.

(1)Ν

in one aspect, η is an integer selected from 1,2, and 3. In a further aspect, η is an integer selected from 1, and 2. In yet a further aspect, η is 3, la an even further aspect, η is 2. In a still further aspect, η is 1.

( 2) I' AND Q

in one aspect, q is i and ρ is 0. In another aspect, ρ is I and q is 0.

In a further aspect, q is 0.5 and ρ is 0.5,

(3) Ζ Groups

r²*, R^2t‘

v

<L ,R'^:

π;

III one aspect, each Ζ is independently selected from hydrogen and R' wherein at least one Ζ is a structure represented by a formula:

R-\ R^2b

vH^-^r3c

\ ηΤ^ρ3ο

R³"

In a further aspect, each Ζ is a structure represented by a formula:

R“ , and

wherein at least one of R^if, R^?i\ R‘^,a, R³¹’, and R^Jv is not hydrogen.

In a further aspect, each Ζ is a structure represented by a formula:

In one aspect, each of'R^u, R^lb, R^w, and R^ld is independently selected from

-~(00}R7\ and Cl*€3 alkyl substituted with 0, i, 2, or 3 groups selected from halogen,

-CN, -SR²⁰, -OR²¹, ~~NR^22aR^22!>, “SCbR²², and “(OO)R²⁴ In a further aspect, each of R^!*‘, R^!b, R^lv, andR‘° is hydrogen.

In a farther aspect, cacti ofR¹*, Rⁱ⁵’, R^k, and R^lu is independently selected from hydrogen, halogen, -CM, -SR²⁰, -OR^2530, -NR^BaR^2B -NR^22aR^22i>lf, -S0₂R^B, and

-(OO)R²*. In a still further aspect, each of R^h\ R^u', R‘^e, and R“° is independently selected from hydrogen, halogen, -CN, -SR²⁰, -OR²’, - SOjR²', and -(C^sO)R'ⁱ⁴. hi yet a further aspect, each ofR‘\ R*^h, R^lt, and R^fii is independently selected from hydrogen, halogen,

-CN, -SR²⁰, and “SChR²³. In an even further aspect, each of R^ia, R*\ R^,c, and R^u is independently selected from hydrogen, halogen, -SR"⁰, and - SCKR^a‘^!. In a still further aspect, each of R^{a, R^th, R^kand R^ki is independently selected from hydrogen, -SR'*, and

-SO?R² '. In yet a further aspect, each of R/^a, R^kI, R*^£, and R^la is independently selected from hydrogen and- SChR²'. In an even further aspect, each of R^!\ R^IX>, R^K, and R*^a is independently selected from hydrogen and -SR*°.

In a further aspect, each of R’^a, R^J\ R^k, and R^s4 is independently selected from hydrogen, halogen, -CN, -OR²¹, -NR^R^”, -NR^R^H^-', and-(OO)R*⁴. In a still fiirther aspect, each of R’*\ R^u>, R^k, and R^:0 is independently selected from hydrogen, -CN,

-OR²⁵. ”NR^22aR^22b, “NR^22aR^22!>H^:, and-(CO)R²⁴. in yet a further aspect, each of R^la, R^f5>, R^!C, and R^ki is independently selected from hydrogen, -OR²¹, ~NR"^aR^22b,

-NR^??aR^2?*H\ and -(OQ)R²⁴. In an even further aspect, each of R^Sa, R^sfe, R^ic, and R^ki ts independently selected from hydrogen, “NR'^{: <a}R'²ⁱⁱ, and -NR^BaR.'^:'^;hlrf. In a still fiirther aspect, each of R^kl, R^tb, R^,c, and Rⁱ⁴ is independently selected from hydrogen and

-NR”"^sR^22bB^:. In yet a further aspect, each of R^ia, R^,:a, R^K, and R¹’" is independently selected from hydrogen and “NR^{i ia}R^22b.

In a further aspect, each of R^la, R^u\ R^t£, and R^!:1 is independently selected from hydrogen, halogen, -CN, -OR²¹, and-(€=0)R²⁴. in a still fiirther aspect, each of R^kl, R^ib, R^k, and R^ki is independently selected from hydrogen, -CN, -OR²*, and -(Ο0)Κ²⁴. In yet a further aspect, each of R’^:a, R^i!>, R^k, and R*^d is independently selected from hydrogen,

-OR"¹, and-(O0)R²⁴. In an even further aspect, each ofR*^a, R^!°, R^JC, and R^k1is independently selected from hydrogen and -(0≈Ο)Κ²⁴. in a still further aspect, each of R^la, R^tb, R^,c, and R*^d is independently selected from hydrogen and -OR"¹.

1« a further aspect, each of R^u\ R^ih„ R^!“, and R^U! is independently selected from hydrogen and halogen. In a still further aspect, each of R^J8, R^is, R^le, and R^ia is independently selected from hydrogen, -Cl, and -~F. In yet a further aspect, each of R’”, R^ti?, R^is, and R^hi is independently selected front hydrogen and-Cl. In an even further aspect, each of R.^Ja, R^fb, R^!C, and R^ki is independently selected from hydrogen and -F.

In a further aspect, each of R^ia, R*⁰, R^ie, and R^!o is independently selected from hydrogen and C1-C3 alkyl substituted with 0,1,2, or 3 groups selected from halogen, -CN,

-SR³'⁰, -OR²¹, -NR^22aR^22b, -S0₂R²³, and -(00)Κ²⁴ In a still further aspect, each ofR^Ja, R^u‘, R.⁵*, and R^hiis independently selected from hydrogen, methyl ethyl /-propyl, and «propyl and substituted with 0, I, 2, or 3 groups selected from halogen, -CN, -SR*⁰, -OR"!

-NR^22sR^22h, ~S0₂R²\ and -(C^:::0)R²⁴, In yet a further aspect, each ofR^ia, R^ib, R^ll and R^h5 is independently selected from hydrogen, methyl, and ethyl and substituted with 0, 1,2, or 3 groups selected from halogen, -CN, -SR™, -GR^2!, -NR^R²™, - S0₂R“\ and

-(O0)R²1 In an even further aspect, each o.fR^ia, R^!b, R⁵*, and R^,e is independently selected front hydrogen and methyl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, -SR²⁰, -OR²¹, -NR²²*R^22b, -S0₂R²⁵, and -CCO)R²⁴.

In a further aspect, each ofR^la, R^tb, R^,v, and R^,a is independently selected from hydrogen and C1-C3 alkyl substituted with 0, 1, or 2 groups selected from halogen, -CN,

-SR'*', -OR²¹, -NR^ii;‘R”^b₅ -S0₂R²‘\ and -(OO)R'⁴, In a still further aspect, each of R^!\ R!^\R^5c, and R^,d ts independently selected from hydrogen and C1-C3 alkyl substituted with 0 or 1 group selected from halogen, -CN, -SR²⁰, -OR^2s,-NR^23aR^22h, -S0₂R^B, and

-(C=0)R²⁴. In yet a further aspect, each of R^kl, R^Jb, R'^c, and R^ki is independently selected from hydrogen and unsubstituted C1-C3 alkyl.

(5) R² Groups

In one aspect, each of R'¹* and R²° is independently selected from hydrogen, halogen, -CN, -SR™ -OR^M,-NR³²*R^32b, -NR^32:lR^32hM^:, -SCfeR³³,-(0==0)Κ™, and Cl-C3 alkyl substituted with 0, 1, 2, or 3 groups selected from halogen, -CN, -SR”'¹, -OR^-><,

-NR^R’™, - SOjRC and-('C=0)R^?4. in a further aspect, each of R'^;!l and R"^y is hydrogen.

la a further aspect, each of R^Ja and IC' is independently selected from hydrogen, halogen, -CN, -SR³⁰, -OR'¹, -NR^3BR^:'²\ -N.R^32aR^32bH\ -S0₂R³'\ and -(C=0)R³⁴. In a still further aspect, each of and R^ib is independently selected from hydrogen, -CN,

-SR³⁰, -OR³¹, -NR^32aR^32b, ~NR^52aR^325>H\ -SOjR” and ~{CO)R^;u In yet a further aspect, each of R~^J and R'° is independently selected from hydrogen, -SR'⁵'⁵, -OR³',

-NR^5?aR^3?i\ -NR^3:?:iR^3ati\ -S0₃R³\ and -(O-G)R³⁴ In an even further aspect, each of R*^a and R³⁵⁵ is independently selected from hydrogen, -SR'\ -OR'⁵⁵, - SCKR^J:', and

- (C“0)R'ⁱ⁴. In a still further aspect, each of R^2a and R^25> is independently selected from hydrogen, -SR‘^<0, and - SO?R'³, In yet a further aspect, each of R‘^;fl and K^3h is independently selected from hydrogen and -SOsRf'l In an even further aspect, each of R^;a and R"^y is independently selected from hydrogen and -SR³⁰.

in a further aspect, each of R'^a and R^a” is independently selected from hydrogen, halogen, ~~CN, -OR³¹, -NR^32aR^32b, -NR^32aR^32bIf, and ™<C-0)R³⁴ In a still further aspect, each of R^aa and R^ib is Independently selected from hydrogen, -CN, -OR'¹,

-NR³²*R^52b, -NR.^33aR^3;!bB.\ and -(COIR³⁴, la yet a further aspect, each of R^3a and R^2b is independently selected from hydrogen, -OR'⁵⁵, -NR^R.'⁵²'⁵, -NR^R'⁵²⁰!!'', and

-{OOfR'f In an even further aspect, each of R^2a and R^Ji? is independently selected from hydrogen, -NR'^R"⁵⁵, and -NR⁵"^aR^;UhH''. in a still further aspect, each of R^3a and R^?b is independenfly selected from hydrogen and - KR^3&R'^,a“H', In yet a further aspect, each of R²* and R³¹' is independently selected from hydrogen and-NR'^aaR^33b.

In a further aspect, each of R^aa and R^a!) is independently selected from hydrogen, halogen, -CN, -OR:'¹, -(C“0)R ’⁴. In a still further aspect, each of R²* and R.'^b is independently selected from hydrogen, -CN, -OR'¹, -(t>0)R'^u. In yet a further aspect, each of R^?B and R'^h is independently selected from hydrogen, -OR'¹, and -(OO)R"⁵⁴. In an even further aspect, each of.R~* and R'^:b is independently selected from .hydrogen and

-(C=0)R^5<!. In a still further aspect, each of R^2a and R³⁵’ is independently selected from hydrogen and -OR³⁵.

In a further aspect, each ofR*^a and R^a0is independently selected from hydrogen and halogen. In a still further aspect, each of R'*⁵ and R^ab is independently selected from hydrogen, -Cl, and -F. In yet a further aspect, each of R^aaand R^2s is independently selected from: hydrogen and -CL In an even further aspect, each of R²* and R.^2b is independently selected from, hydrogen and -F.

In a further aspect, each of R*^a and R^a” is independently selected from hydrogen and G1-C3 aikvl substituted with 0, 1,2, or 3 groups selected from halogen, -CN, -SR'°,

-OR' \ -SO?R^v, and -(OOfR'l In a still further aspect, each of R²* and R^2b is independently selected from hydrogen, methyl, ethyl, /-propyl, and n-propyl and substituted with 0,1, 2, or 3 groups selected from halogen, -CM, - SR'°, -OR³’,

-NR^32aR^32b, -S0₂R^B, and ~(CO)R³⁴ in yet a further aspect, each of R²* and R^2!) is independently selected from hydrogen, methyl, and ethyl and substituted with 0, 1, 2, or 3 groups selected from halogen, -CM, -SR³⁹, -OR³’, -NR^55aR.^m-SQjR³³, and

-CC=0)R'^u, In an even further aspect, each of R^3a and R^2b is independently selected from hydrogen and methyl substituted with 0, 3,2, or 3 groups selected from halogen, -CN,

-SR³⁰, -OR³’, ~NR^32aR^32b, -SQ?.R³³, and Ηθ-0)Κ³⁴

In a further aspect, each of R^aa and R*° is Independently selected from hydrogen and C1-C3 alky! substituted with 0, i, or 2 groups selected from halogen, -CN, -SR'⁵°,

-OR³¹, -NR^32aR³²ⁱ; -SOjR³³, and -(Ο0)Κ³⁴ In a still further aspect, each of R^3s and R²” is independently selected from hydrogen and C1-C3 alkyl substituted with 0 or 1 group selected from halogen, -CN, -SR''⁰, -OR'*, - NR:^!'^iaR'^2!>, -SO?R^JJ, and -(OO)R'’⁴. In yet a further aspect, each of R"^J and R'^:a is independently selected from hydrogen and unsubsMured C1-C3 alkyl

In a further aspect, R^2a is hydrogen and R"^b is selected from halogen, -CN,

-SR³⁰, -OR³’, -NR^32aR^32b, -NR^;i25R^32bH", -S0₂R^X!, ~-(O0)R³⁴, and Cl -C3 alkyl substituted with 0,1, 2, or 3 groups selected from halogen, -CM, -SR'ⁿ⁾, -OR**,

-NR^5JaR^32a, -S0₂R³³, and - (0=0)Κ^. In a still further aspect, R^2a is hydrogen and R^2b is selected from halogen, -CN, -SR³”, -OR'⁵, ~NR^32aR^m, ~NR^33aR^32bH^:, -S0₂R³³, and

-(0≈0)Η³⁴. In yet a further aspect, R^3s is .hydrogen and R^2b is selected from-CN, -SR'*⁵,

-OR³⁵, -NR^32aR^32b, -NR^32aR^32bH*, -SOjR³³, and HOO)R³⁴. hi an even further aspect, R^2a is hydrogen and R^a is selected from -SR⁵⁰, -OR³’, -NR^32aR^32b, -NR^32aR^32bH‘\

-S0₂R'', and -(C~0)R^j4. In a still further aspect, R^;a is hydrogen and R^2b is selected from

-SR³⁰, -OR³’, -S0₂R³³, and ~(CO)R³⁴In yet a further aspect, R^2a is hydrogen and R^2b is selected from - SR'° and- SOjR". In an even further aspect, R^<!! is hydrogen and R²ⁱ' is

-SOjR³'\ In a still further aspect, R^2a is hydrogen and R'^:b is -SR³⁰

In a further aspect, R^2a is hydrogen and R'^b is selected from halogen, -CN,

-OR3^1, “NR^32aR^32b, -NR^5?aR^32l>H", and -<C>0)R³⁴. In a still further aspect, R^2a is hydrogen and R^2bis selected from -CN, -OR³¹, ~NR^32i!R^32b, -NR³²³R^32bHy and

-(C^:::0)R"l In yet a further aspect, R*'¹ is hydrogen and R^ih is selected from-OR^-51,

-NR'"^aR^;'^2!r'_f , and -t C“0).R'⁵⁴, in an even further aspect R*¹ is hydrogen and R^2b is selected from -NR'^u*R'’^2b and in a still further aspect, R~^J is hydrogen and R"^:' is -NR³'^JR³"^l>ir, In yet a further aspect; R** is hydrogen and R^J> is -NR'^R'*'^l\

in a further aspect, R²* is hydrogen and R~^b is selected from halogen, -CN,

S -OR-’'¹, and -(C^::=Q)R'⁴. In a still further aspect, R'^;il is hydrogen and R^2b is selected from

-CN, -OR’¹, and-fC^OjR’⁴. In vet a further aspect, R²⁴ is hydrogen and R~^b is selected from -OR⁰¹ and -~(C“0)R^:'⁴. in an even further aspect, R*⁴ is hydrogen and R** is

-(C^:::0>R’3 In a still further aspect, R ' is hydrogen and R^h is -QR^>f.

in a further aspect, R^2a is hydrogen and R'^b is halogen. In a still further aspect, it) R^2a is hydrogen and R^ab is selected from -Cl and -F. In yet a further aspect, R"^;‘^l is hydrogen and R^a is -Cl. In an even fiirther aspect, R³* is hydrogen and R^2b is - Ρ.

In a further aspect, R^2b is hydrogen and R^a is Cl <3 alkyl substituted with 0, 1, 2, or 3 groups selected from, halogen, -CN, -SR⁴; -OR.'’¹, -NR'^2,!R'^i3b, - SOdC; and

-{C^::<>)R⁴⁴, In a still further aspect, R'³ is hydrogen and R^?b is selected from, methyl, ethyl, {5 (“propyl, and w-propyl and substituted with 0, 1,2, or 3 groups selected from halogen, -CN,

-SR³⁰, -OR³¹, -NR^s2aR^33b, -SO#⁵², and -<C=0)R³⁴. In yet a further aspect, ,R^2a is hydrogen and R^at> is selected from methyl and ethyl and substituted with 0,1, 2, or 3 groups selected from halogen, -CN, ~SR^M’, -OR^Ji,-NR^32aR^321>, -SCKR³³, and-{C><))R^:H In an even fiirther aspect, R^2a is hydrogen and R^J<0 is methyl substituted with 0, I, 2, or 3 groups 20 selected from halogen, -CN, -SR'^,(>, -OR³', -NR'^R^:Ut; -SO#"', and-{O0)R'⁴.

In a further aspect, R²* is hydrogen and R^2b is C1-C3 alkyl substituted with 0, .1, or 2 groups selected from halogen, -CN, -SR'”¹, -OR’¹, -NR''^aaR^a2b, - SO#", and

-(€=^:Q)R³⁴. In a still further aspect, R^2a is hydrogen and R'^:b is C1-C3 alkyl substituted with 0 or 1 group selected from halogen, -CN, -SR'°, -OR'’¹, -NR'^43aR^32b, -SO#⁴³, and

25 -(C=0)R^J4. In yet a further aspect, R^3s is .hydrogen and R^2tt is unsubsrituted C1.-C3 alkyl.

in one aspect, at least one ofR²*, R^Jls, R'^,a, R* and R'^£ is not hydrogen.

(6) R³ Groups

In one aspect, each of R'\ R^3b, and R⁴⁴ is independently selected from hydrogen, halogen, -CM, -SR⁴⁰, ™<3R⁴¹, -NR^42aR⁴²\ -NR⁴“^aR^42,,H \ -S0₂R⁴\ and -(Ο=0)Κ⁴⁴. In a further aspect, each of II¹'⁴, and R^,v is hydrogen,

In a further aspect, each of R"‘\ R'\ and R^;,c is independently selected from hydrogen, ~CN, -SR⁴⁰, ~<)R⁴¹, -NR^42aR⁴²\ -NR^42aR:^!;!bK^:, -SOjR⁴³, and -(CO}R⁴⁴. In a still further aspect, each of R³⁴, R'^0>, and R"^>c is independently selected from hydrogen,

-SR⁴⁰, -OR⁴¹, ~NR;^i2aR⁴²\ -NR⁴²³R^4a,I-r; -SQ?R⁴\ and -f(M))R⁴⁴. In yet a further aspect, each of R^>f“, R^:>b, and R'° is independently selected from hydrogen, -SR⁴⁰, -OR⁴¹,

-SO2R⁴', and -(C=0)R⁴⁴. In an even further aspect, each of R"\ R^?4J, and R^ is independently selected from hydrogen, -SR⁴⁰, and -SCFR⁴'. In a still further aspect, each ofR”, R‘^,b, and R.'^k‘ is independently selected from hydrogen and -SO;?R⁺‘^!. In yet a further aspect, each of R^,J, R^3b, and R^JC is independently selected from hydrogen and - SR⁴⁰.

In a further aspect, each of R^ia, R^!\ and R³* is independently selected from hydrogen, -CN, -OR⁴¹, ~NR^42aR^42b, -NR^43aR^42bH^r, and -{C-OsR⁴⁴. In a still further aspect, each ofR"'*, R^,b, and R^3u is independently selected from hydrogen, -OR⁴¹,

-NR^42aR^42b, -NR^42aR^42bl-r, and -<C-0)R⁴⁴. In yet a further aspect, each of R’^a, R^5b, and R* is independently selected item hydrogen, ™NR^42sR^42b, arid ~NR^42aR^42bB \ In a still further aspect, each of R^1a, R³⁰ and R-^>e is independently selected from hydrogen and

-NR^44aR^42bH^!. In yet a further aspect, each of R'\ R^JS, and R'^,e is independently selected from hydrogen and -NR^R***.

In a further aspect, each of R'⁴, R'^b, and R^,c is independently selected from hydrogen, -CN, -OR⁴’, and-(C-O/R⁴⁴, in a still further aspect, each of R^3s, R^!b, and R³* is independently selected from hydrogen, -OR⁴¹, and - (C=^:::0)R⁴⁴. In yet a further aspect, each of R^3s, R'^n>, and R:^!C is independently selected from hydrogen and -(C>0)R⁴⁴, In an even further aspect, each of R'^,a, R'⁰, and R^M is independently selected from hydrogen and

-OR¹ .

In a further aspect, each of R'h R^;n>, and R³*" is independently selected from hydrogen and halogen, hr a still further aspect, cadi of R’^;i, R⁴¹¹, and R^3c is independently selected from hydrogen, -Cl, and -F, In yet a further aspect, each of R'\ R^jb, and R³⁴ is independently selected from hydrogen and -Cl. in an even further aspect, each of R^Ja, R'^,b, and R^je is independently selected from hydrogen and -F.

In a further aspect, R^;,x is hydrogen and each of R"'\ and R^;,c is independently selected from halogen, -CN, -SR⁴⁰, -OR⁴⁵,™NR^42aR^42b, -NR*^2aR^42l>H\ ™SO?R^4J, and

-(0≈Ο)Κ4⁴ In a still further aspect, R/¹³ is hydrogen and each ofR'^<b, and R/^,c is independently selected from~CN, -SR⁴⁰, -OR⁴¹, -NR^42aR^42b, ~NR^42aR^42S>H\ ~S0₂R⁴³, and -(0≈0)Κ⁴⁴. In yet a further aspect, R'^,a is hydrogen and each of R^JS, and R'^,e is independently selected from -SR⁴⁰, -OR⁴ⁱ,-NR^42aR^421>, -NR^42aR^42bIT, -S0₂R⁴l and

-(C=0)R⁴⁴. In an even further aspect, R"^>s is hydrogen and each of R'^fc, and R‘^,c is Independently selected from -SR⁴⁰, -OR⁴⁴, ™SO?R⁴\ and -{0==0)R⁴⁴. In a still further aspect, R^ja is hydrogen and each of R^3b, and R‘^H‘ is independently selected from -SR⁴⁰ and

-SOjR⁴³.

In a further aspect, R^,a is hydrogen and each of R'^b, and R^>£ is independently selected from halogen, -CN, -OR⁴⁴, -NR^42sR^4a, -NR^43aR^4JbH\ and -(Ο≈0)¾⁴⁴. In a still further aspect, R^Ja is hydrogen and each of R ’^i?, and R'^!c is independently selected from

-CN, -OR⁴¹, ~NR^43aR^42b, -NR^42aR^42bH\ and ~Ct>0)R⁴⁴, in yet a further aspect, R^3a is hydrogen and each of R'^lb, and R^ae is independently selected from-OR⁴¹, -NR^42sR^4at>,

-NR^R⁴⁴⁰!!', and -(00)R.⁺⁴. In an even further aspect, R^ja is hydrogen and each of R'^iS), and R^3c is independently selected from -NR^42aR^42h and -NR^42ilR^42t?Hh

In a further aspect, R^a:! Is hydrogen and each of R'y and R^;Sc is independently selected from .halogen, -CN, -OR⁴¹, and-(OO)R⁴⁴. In a still further aspect, R'⁵* is hydrogen and each of R~^lb, and R'° is independently selected from -CN, -OR*¹, and

-(OO)R.⁴⁴. In yet a further aspect, R:ⁿⁱ is hydrogen and each of R^Sb, and R"^c is independently selected from-OR⁴⁴ and-(C^:::0)R⁴⁴.

In a further aspect, R^JS is hydrogen and each of R'⁰, and R^5C is halogen . In a still further aspect, R^Ja is hydrogen and each of R^;ib, and R^je is selected from-Cl and -F. In yet a further aspect, R^3a is hydrogen and each of R'^,b, and R^JC is -Cl. In an even further aspect, R’^a is hydrogen and each of R'¹¹’, and R³*' is -F.

In a further aspect, each of R^y,‘ and R^>:' is hydrogen and R^>e is selected from halogen, -CN, -SR⁴⁰, -OR⁴¹. -NR^42aR^42b, -NR^42aR^42bif. -SO-jR⁴³, and ~(C=0)R⁴⁴, In a still further aspect, each of R‘^,a and R’^bis hydrogen and R^,v is selected from -CN, -SR⁴⁰,

-OR⁴¹, -NR^42aR⁴²\~NR^42aR^42bH \ ~S0₂R⁴³, and -(OO)R⁴⁴. In yet a further aspect, each of R'^J and R^J0 is hydrogen and R'^e is selected from “SR⁴⁰, --OR⁴', -NR^44!iR^4ib,

-NR^4?aR^4?i>H\ “S0₂R^4J, and -{C-Q)R'^M In an even fiirther aspect, each of R^bs and R^,b is hydrogen and R^v is selected from -SR*⁰, -OR⁴’, -SOiR⁴"', and -(00)R⁴⁴. In a still further aspect, each of R^ja and R'^b is hydrogen and R^ is selected from -SR⁴¹' and

-SOjR⁴⁴. In yet a further aspect, each of R^,;!and R.^ib is hydrogen and R.^ie is -SOjR^’. In an even further aspect, each of R'^,a and R‘^,b is hydrogen and R‘^,e is -SR⁴⁰.

In a further aspect, each of R^Mand R^!!> is hydrogen and R"^te is selected from halogen, -CN, -OR⁴*, -NR⁴²⁸R^42&, -~NR^42aR⁴²¹W, and -(OO)R⁴⁴. In a still further aspect, each ofR³* and R^,b is hydrogen arid R* is selected from -CN, -OR⁴¹, -NR⁴²*R^42b,

-NR^42aR^42hE\ arid ~{0=0)R⁴⁴. in yet a further aspect, each of R^3:l and R^3b is hydrogen and R^?c is selected from-OR⁴', -NR^42aR^4Jfi, -NR⁴²*R⁴²1r, and -(CO)R⁴⁴. In m even further aspect, each of R'^a and R^jb is hydrogen and R.'^,e is selected from- NR^42aR^4,iS5 and

-NR^R⁴*!:!'. In a still further aspect, each of R'^is and R'^b is hydrogen and R'¹ is

-NR⁴"^aR^42eH''. In yet a further aspect, each ofR^:>a and R^Ah is hydrogen and R"'⁰ is

-NR^43sR^42b

In a further aspect, each of R^3a and R^J" is hydrogen and R^?v is selected from halogen, -CN, -OR⁴*, and-(OO)R⁴⁴. In a still further aspect, each of R:^,a and R^:!f> is hydrogen and R^JC is selected from-CN, -OR⁴¹, and -(OO)R⁴⁴. In yet a further aspect, each of R^,a and R^>h is hydrogen and R'^tc is selected from-OR⁴’ and-(O0)R⁴⁴. in an even further aspect, each ofR⁴⁸ and R'^b is hydrogen and R'^>£ is -(OQ.lR⁴*. In a still further aspect, each of R^JiI and R'^bis hydrogen and R'^v is -OR⁴¹.

In a further aspect, each of R^Sli and R^3bis .hydrogen and R^ is halogen. In a still further aspect, each ofR’⁴ and R‘^,n is hydrogen and R‘^>e is selected from-Cl and- F. In yet a further aspect, each of R’'¹ and R‘^!!' is hydrogen and R‘^H‘ is -Cl. In an even further aspect, each ofR” and R^3b is hydrogen and R^2t is -F.

In one aspect, at least: one of R^4S, R^ib, R’⁴, R^ib, and R‘^H' is not hydrogen.

(7) R²Vr^js,a.nd R²²Groups

In one aspect, each of R'^:0, R^2!, R^{: ;i}\ and R'^;2\ when present, is independently selected from hydrogen, C1-C3 alkyl C.1-C3 monohaloalkyl andCl-C3 polyhaloalkyl In a further aspect, cacti of 11"°, R*^!, Rⁱ²⁸ and R²ⁱ*, when present, is hydrogen.

In a further aspect, each of R^a0> R^a\ R*²\ and when present, is independently selected from hydrogen, Ci-03 monohaloalkyl, and CI-C3 polyhaloalkyl. In a still further aspect, each of R^3u, R"^;\ R^2js, and R²"²', when present, is independently selected from hydrogen, -C%F, -CM, -ClfrCIRF, ~CH₃CH₂Cl ~€HFj, ~CH₂CHF₂,

-CFj, -CH₂CF₃, CHCIj, -CHjCHCb, -CCk and -CFFCCk In yet a further aspect, each of R^2<), R^2!, R.'^;2a, and R^¹’, when present, is independently selected from hydrogen,

-CHP₂, -CH₂CHP₂, -CFj, -CH₂CF_3j -CHCk, -OkCHCl, ™CCh, and -CH₂CCi₃. In an even further aspect, each ofR^’, R^al R“*'\ and R^2il>, when present, is independently selected from hydrogen, ™CF,, -CH₂CF₃, -CClj, and -CFRCCk

In a further aspect, each of R"^:i!, R^?!, R.^aa, and R^-Uh, when present, is independently selected from, hydrogen, and C1.-C3 alkyl. In a still further aspect, each of R²⁰, R²ⁱ, R²²*, and .R^a2b, when present, is independently selected, from .hydrogen, methyl, and ethyl. In yet a further aspect, each of R^ai\ Rk R^ak and R^a2b, when present, is independently selected from hydrogen and methyl

In a further aspect, R²⁰, when present, is hydrogen and each of R*¹, R'⁵'⁵⁸, and R2^2a, when present, is independently selected from CI-C3 alkyl, C1-0 monohaloalkyl, and CI-C3 polyhaloalkyl. In a still further aspect, R"^:0, when present, Is hydrogen and each of R²ⁱ, R²²l and when present, is independently selected from €1-0 monohaloalkyl, and C1-C3 polyhaloalkyl In yet a further aspect, R^Jk when present, is hydrogen and each, of R^2!, R"^;k and R.^m, when present, is .independently selected from -€H₂F, -CffrCl,

-CH2_CH2_F, -CH₂CH₂Cl, -CHF₂, -CH₂CHF₂, -CF_3s -CH.2CF3, CHCl, -CllCHCl.

-CCI3, and ~~€H₂CCk hi an even further aspect, Rk when present, is hydrogen and each of R²¹, R“^a, and Rⁿ\ when present, is independently selected from ™CHF₂, ™CH₂CFiF₂,

-C.F;i, -CH-₂CFs, -CHCIj, - CH2CHCI2, -CCIj, and -CHjCCU. In a still further aspect, Rⁱ⁰, when present, is hydrogen and each of R^al, R^a2<!, and R:^2b, when present, is independently selected from -~CFs, -~Qi₂CF.% -~CCi₂, and ~~CH?€CI ?.

In a further aspect, R^2,), when present, is hydrogen and each ofR²', and R²^ when present, is CI-C3 alkyl. In a still further aspect, R²⁰, when present, is hydrogen and each of R'^:t, R’^{i J}, and R'ⁿ‘, when present, is selected from methyl and ethyl. In yet a further aspect, R*¹, when present, is hydrogen and each of R“\ R"^a, and R^iib, when present, is methyl.

In a further aspect, R²ⁱ, when present, is hydrogen and each of R^2w, and R^22b, when present, is independently selected from CI-C3 alkyl, CI-C3 monohaloaikyi, and CI-C3 polyhaloalkyl, In a still further aspect, R³*, when present, is hydrogen and each of R^3i>, R^22a, and when present, is independently selected from CI-C3 monohaloaikyi, and CI-C3 polyhaloalkyl. In yet a further aspect, R^al, when present, is hydrogen and each ofR^8U, R“^a, and R?^2!>, when present, is independently selected from -~CH₂F, -~Cf FCI,

-CFRCFtiF, -CH₂CH₂C1, -CHF₂, -CH₂CHF₂, -CF_s, -CH₂CF₃, -CHC1₂, -CH₂CHC1₂, CCI;, and -CFbCCl. In an even further aspect, R²¹, when present, is hydrogen and each of R~'\ R“^a, and when present, is independently selected from -CHF₂, -CH₂CHF₂,

-CF?_,-CH₂CF₃, -CHCl₂, -CH₂CRCi₂, -CCl₃, and -CH₂CC1j. in a still further aspect, R^Ji, when present, is hydrogen and each of R^a0, R^33b, and R^m, when present, is independently selected from ™CF_?, -Oi₂CF₃, -CCl₃, and -OfcCCfe.

In a further aspect, R²ⁱ, when present., is hydrogen and each of R^A>, R‘‘^a, and R^22b, when present, is CI-C3 alkyl. In a still further aspect, R~^{, when present, is hydrogen and each of R'^:0, R'^2a, and when present, is selected from methyl and ethyl, in yet a further aspect, R^?>, when present, is hydrogen and each of R'^:0, R"³⁸, and R"^Jii, when present, is methyl.

In a further aspect, R²²*, when present, is hydrogen and each of R²ⁱ⁾, .R^2!, and R^2ah, when present, is independently selected from C1-C3 alkyl, C1-C3 monohaloaikyi, and Cl*C3 polyhaloalkyl. In a still further aspect, R’¹*'¹, when present, is hydrogen and each of R²’\ R³*, and R'^;a\ when present, is independently selected from C1-C3 tnono.haioai.kyl, and C1-C3 polyhaloalkyl. In yet a further aspect, R~^aa, when present, is hydrogen and each of Rⁱ⁰, R²⁵, and R*^2b, when present, is independently selected .from ~CH₂F, -CHhCl,

••••01.01,1'. “CH;jCH_:jCI, ----C UT . -“CHjCHFj. ----ΠΤ, -CH₂CF₃, -CHCF, --CHTTfCk

-€C13_, and -CH₂CCl,y In an even further aspect, R^2?\ when present, is hydrogen and each of R"^;>), R^?!, and R^a3b, when present, is independently selected from: -CH.Fj, -~CFf₂CHF₂,

-CFs, -CH₂CF₃, “CHCh, -CH₂CHCi_2>-CCh, and -CHfeCCH. In a still further aspect.

R²²*, when present, is hydrogen and each of R²⁰, R^2J, and R^22t>, when present, is independently selected .ffom~CF$, -CH2CF3, -CCis, and-CfibCCU.

In a further aspect, R²²\ when present, is hydrogen and each of R²⁰, R²¹, and R^2il>, when present, is CI-C3 alkyl In a still further aspect, R^a2<t, when present, is hydrogen and each of R'*, R’^a, and R²'²’, when present, is selected from methyl and ethyl. In yet a further aspect, R"²®, when present, is hydrogen and each of R²⁰, R²ⁱ, and when present, is methyl.

In a further aspect, each of R'**’ and Rfwhen present, is hydrogen and each of R/^U:’ and R‘^;‘^A, when present, is independently selected from C1-C3 alkyl, C1-C3 monohaioalkyl.. and CI-C3 polyhaloalkyl. In a still farther aspect, each of R^a> and R^?!, when present, is hydrogen and each of R"^;'^;a and R^22b, when present, is independently selected from C1-C3 monohaioalkyl, and C1-C3 polyhaloalkyl In vet a further aspect, each of R“⁽¹ and R^af, when present, is hydrogen and each of R^a2i‘ and R^aab, when present, is independently selected from -CM₂F, -CH₂Cl -CH₂CM₂F, -CH₂CH₂€L ~CHF₂,

-CHjCHFj, ~CF₂, -CH2CF3, -CHCF, -CfFCHCF, -CCF, and -CHjCCh. In an even further aspect, each of R^JJ and R²ⁱ, when present, is hydrogen and each of R*^2<! and R^a2b, when present, is independently selected from -CHFj, “CH₂CHF₂, -CFj, -CH2CF3, ~CHCl, ~CH₂CHCl, -CCU, and -CfbCCIy In a still timber aspect, each ofR²⁰ and R²¹, when present, is hydrogen and each of R'¹'* and R^’, when present, is independently selected from -CF₃, “CH₂CF₂, -CCU, and -C.H2CCI3.

In a further aspect, each ofR^2b and R“\ when present, is hydrogen and each of R'^:Us and R^aab, when present, is C1-C3 alkyl. In a still further aspect, each of R²⁰ and R^a, when present, is hydrogen and each of R^:;a and R^’, when present, is independently selected from methyl and ethyl In yet a further aspect, each of R²⁰ and R“‘, when present, is hydrogen and each ofR^⁴ and R“^b, when present, is methyl

In a further aspect, each of R^a’, R*^!, and R“⁴is hydrogen and R^2ai> Is selected from C!*C3 alkyl, Cl*C3 monohaioalkyl and 0-0 polyhaloalkyl In a still further aspect, each ofR.'^;<!, R^?t, and R"'⁴ is hydrogen and R^:'^:!,is selected from C1-C.3 monohaioalkyl, and CI-C3 polyhaloalkyl. In yet a further aspect, each of R^a!, R"\ and R²ⁱ* is hydrogen and R*^2b is selected from -CBjCl -CH₂CH?.F, ™CH₂CH;>C1, ™CBF₂, ™CH?CHFj, ~CF₂,

-CH2CF3, -CHC1₂, -CHjCHCIj, -CCh, and -CH2CO3. In an even further aspect, each of R~'\ R²’, and R"³ is hydrogen and is selected from -CHF?, -CHjCHF?., -CF.j,

-CH2CF3, -CHCl, -CHjCHQ;?. -CCft, and-CHjCClj. In a still further aspect each of R⁴⁰, R^2>, and is hydrogen and R'^;bis selected from -CFj, -CH2CF3, -CCft, and

-CH2CCI3.

In a further aspect, each of R^3<1, R^?!, and R^2?i* is hydrogen and R^22h is C1-C3 alkyl. In a still ftirther aspect each of R²⁰, R²⁵, and R²²* is hydrogen and R^22!> is selected from methyl and ethyl In yet a ftirther aspect, each of R^4tl, R" *, and R^¹ is hydrogen and R^is methyl.

(8) R²³an» R²⁴ Groups

In one aspect, each of R'^J and R²⁴, when present, is independently selected from

-O',-OR²⁵, C1-C3 alkyl,CJ-C3 monohaloalkyl,C1-C3 polyhaloalkyl, and-NR²⁴⁸R^2{tt\ In a fnrther aspect each of R^B and R²⁴, when present, is independently selected from-O’,

-OR²⁵, and -NR^R²**. In a still further aspect, each of R^;> and R²⁴, when present, is independently selected from-OR²⁴ and -NR^2fiaR^?4b. In yet a Either aspect, each of R^B and R"⁴, when present, is -OR²⁵, In an even further aspect, each of R^B and R²⁴, when present, is -NR^R'³*.

in a further aspect cadi of R^B and R²*, when present, is independently selected from CI-C3 alkyl, CI-C3 monohaloalkyl, and C1-C3 polyhaloalkyl. In a still further aspect each ofR²"⁴ and R"'\ when present, is independently selected from methyl, ethyl, -CH2F,

-CM, -CFftCftftF, “CHjCfftCl, -CHF₂, -CFftCHF?, -CF₃, -ΠΚΤη -CHCft,

-CH2CHCI2, -CGIs, and -CH2CCI3. In yet a further aspect, each of R²' and R"^;4, when present, is independently selected from methyl, -€H;F, -€H>C1, -CHFj, -CFj, -CHCft, and -€Cft,

(9) R²⁵AN!) R^2{* GROUPS

In one aspect, each of R³"', R^, and R*^6fc, when present, is independently selected from hydrogen, C1-C3 alkyl, Cl -C3 monohaloalkyl, and C1-C3 polyhaloalkyl. In a further aspect, each of R'^;\ R'^;fss, and R²"¹’, when present, is hydrogen.

In a further aspect, each of R^B, R*⁴⁸, and R^3!ft, when present, is independently selected from hydrogen, CI-C3 monohaloalkyl, andC.l-C3 polyhaloalkyl. in a still further aspect, each of R~\ R²**,, and R^2U', when present, is independently selected from hydrogen, ~~CH₂F, -CHjCI, ™CH₂CH₂F, -OfcCHiO, -CHF₂, -CH₂CHF₂,~~CF_h ~€H jCF_:?,

-CHC1₃, -ClfrCHCh,~€Ch, and -CHjCCfe. In yet a further aspect each ofR²⁵, R^K\ and Rr"\ when present, is independently selected from hydrogen, ~CH₂F, ~-CH₂Cl, ~CHF2_, “CF_3j ~~CHCJ₂, and ~CCh.

In a further aspect, each of R³\ R^2t* and R"'*, when present, is independently selected from hydrogen and C.1-C3 alkyl In a still further aspect, each of R²⁵, R^i<!\ and R^A,S when present, is independently selected from hydrogen, methyl and ethyl, in yet a further aspect, each of Ri"', R⁴**, and R*¹*, when present, is independently selected from hydrogen and methyl.

In a further aspect, R²⁵ is hydrogen and each of and R^2ftb is independently selected from C1*C3 alkyl C1*C3 monohaioaikyl and C1-C3 polyhaloalkyi. In a still further aspect, R*⁵ is hydrogen and each of R*^r:,<> and R^3nt> is independently selected from Cl* C3 alkyl, C1.-C3 monohaioaikyl, and CI-C3 polyhaloalkyi. in yet a fiirther aspect, ft*⁵ is hydrogen and each of R*²'³ and R^i6i> is independently selected from methyl, ethyl, -CH;>F,

-CHjCl, -CHjCHjF, -~CFIjCH_:jCl, -~CHF_?„ -CHjCHF?, ~€F_;5, -CikCF,, -CHCl₂,

-CH₂CHC1₂, -CCI5, and -CH₂CCIj. In an even further aspect, R"⁵ is hydrogen and each of R²*³ and R²* is independently selected from methyl.~€H₂F, ~€H₂C1. -CHF₂. -CF_?,

-CliCh, ~CCk

In a further aspect, R** is hy drogen and each of R^2s and R^2<* is independently selected from CI-C3 alkyl, C1-C3 monohaioaikyl, and C.1-C3 polyhaloalkyi In a still further aspect, R'*^a is hydrogen and each of R” and R^i6b is independently selected from C1 C3 alkyl, CI-C3 monohaioaikyl, and Ci~C3 polyhaloalkyi. In yet a further aspect, R^K'³ is hydrogen and each of and R^2t* is independently selected from methyl, ethyl, -~CH₂F,

-CH2_CL -Cl-frCt-fcF, -Πℓ;Π1;:Π. ~CHF_2s ™CH₂CMF₂, ~CF₃, -CFFCF;. -CHCfr,

-CH₂CHC1₂, -CCls, and -CH2CCI3. In an even further aspect, R^:,>3 is hydrogen and each of R²⁵ and R^A,S is independently selected from methyl, ~-€H₂F, -CFI^Cl, -“C’HFj, ~~CFj,

-CHCF, and-CCk.

In a further aspect, each of R*' and R^3,,a is hydrogen and R:'^A is selected from CI-C3 alkyl, C F-C3 monohaioaikyl, and C1-C3 polyhaloalkyi. In a still further aspect, each ofR²⁵ and R²*’⁸is hydrogen and R^3<* is selected from methyl, ethyl, -CH₂F, -CH₂CI, ~~CH₂CH₂F, -CI-bCIHCl -CHF;?, -CHjCHFj, -CFj, -CHjCFs, -CHOb, -CH₂CHCl>,

-CCI3, and “CH2CCI3. In yet a further aspect, each of R~^J and is hydrogen and R^itb is selected from methyl, ~~CH,F, -CH₂CI, -CHFj, -CF3, -CHCfe, and -CCI3.

(10) R³⁸, R³\ Am R^3J Groups

In one aspect, each ofR"’⁸, R'h R^jja, and R^Jib, when present, is independently selected from hydrogen, Ci-C3 alkyl, Cl -03 monohaloalkyl, and CI-C3 polyhaloalkyl. In a further aspect, each ofR^3u, R^>J, R^33a, and R^J'^:b, when present, is hydrogen.

In a further aspect, each ofR³⁸, R³ⁱ, R³²*, and R^’, when present, is independently selected from hydrogen, C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl hi a still further aspect, each of R'°, R^J!, R'"⁰, and when present, is independently selected from hydrogen, -CH₂F, -CHjCl -CH,CH,F, -CH₃CH₂C1, -CHF,, -CH₃CHF₃,

-CF_3s -~CH₂CF_3> -CHCl>, -Cl-RCHCb, ~CCh, and -CI-FCClc In yet a further aspect, each of R³⁰, R'ⁿ, R^33a, and R^0_a, when present, is independently selected from hydrogen,

-CHF,, -CH3CHF3, -CF3, -CHjCF,, -CHOj, -CH,CHCi,, -CCF, and -CH₃CCi₃. In an even further aspect, each of 1C'⁵, R'^1,:, 1C⁰¹, and R^3a*„ when present, is independently selected from hydrogen, -CFj, -CFFCFh, -CCU, and -Q-FCC1,..

in a further aspect, cadi of R^3tJ, R^0t, and R⁰'^a, when present, is independently selected from hydrogen and C1-C3 alkyl In a still further aspect, each of R^;i0, R^ji, R^;i2"', and R’"^b, when present, is independently selected from hydrogen, methyl, and ethyl. In yet a further aspect each of R‘^!t), R”, R⁰'⁵⁸, and R^;(2b, when present, is independently selected from hydrogen and methyl.

In a further aspect, R’°, when present, is hydrogen and each of R'^vl . R^3?a, and R^, when present, is independently selected from Cl-C3 alkyl, C1-C3 monohaloalkyl, and C1-C3 polyhaloalky l. In a still further aspect, R'* when present, is hydrogen and each of R.;^''!^, R^3J\ and when present, is independently selected from CI-C3 moaohaioalkyl, and C1-C3 polyhaloalkyl. In yet a further aspect, R'¹', when present, is hydrogen, and each ofR’¹, R'¹⁰⁰, and R^, when present, is independentiy selected from-CHjF,-CHjCl,

-ΠΚΗΗ·. -CH,CH,Ci, -CHF,, -CHjCHFj, -CFj, -CFbCFy -CHCF. -ClFCHCb.

-CCI3, and -C'HjCClj. In. an even further aspect, R'^!\ when present, is hydrogen, and each of R'^1!, R^00i>, and R:^,"^l>, when present, is independently selected from -CHF,, -CFFCHF,, ”CF₅, -CH2CF3, -CHClj, -ClFCHClj, -CCR, and ™℮Μ,℮℮1,. In a still further aspect, R^>0, when present, is hydrogen and each of R'¹ ’, R'"⁰, ami R'"’’’, when present, is independently selected .from-CFs, -CH2CF3, -CCl?, and-CH₂CCl.j.

hi a further aspect, R^;,°, when present, is hydrogen and each of R^M, R^u* and R^3il\, when present, is CI-C3 alkyl hi a still further aspect, R'^il!, when present, is hydrogen and each ofR'*’, and R⁰³ⁱ', when present is selected from methyl and ethyl. In yet a further aspect, R'°, when present, is hydrogen and each of R.'^>J, R'~^a_s and R'^2b, when present, is methyl.

in a further aspect, R^;,i, when present, is hydrogen and each of R'°, R^Ji* and when present is independently selected from C1-C3 alkyi, CI-C3 monohaloalkyl, and CI-C3 polyhaloalkyl. In a still further aspect, R'l when present, is hydrogen and each of

R^f and R''^:b, when present, is independently selected from €5-0 monohaloalkyl, and C1-C3 polyhaloalkyl In yet a further aspect, R''^!, when present, is hydrogen and each of R^,(>, R^⁸,, and R^m, when present, is independently selected from -CH?F, -CHjCl, “CHiCHjF, -CHjCHjCl, -CHF₂, -€H₂CBF₂, -CF₃, -CJHhCFs, -CHCh, -C%CHCF,

-CCl3, and-CHfeCCb. hi an even further aspect, R'*, when present, is hydrogen and each ofR'^w, R’*⁰, and R^>ib, when present, is independently selected from .-CHF_2> -CHjCKP;?,

-CF₃, -CH₂CFs, -CiiCk' -CH₂CHCi₂, -CCk, and ~€H₂CCh. In a still further aspect, R:^>!, when present, is hydrogen and each of R^JW, R'²⁰, and when present, is independently selected .from-CFs, -CH2CF3, -C(%, and-CH-jCClj.

hi a further aspect, R -’, when present, is hydrogen and each of R'°, R'⁵”³, and R"^2il, when present, is C1-C3 alkyl In a still further aspect, R'^u, when present, is hydrogen and each ofR’^<u, R'^va, and R^uh, when present, is selected from methyl and elhyl, In yet a further aspect, R^ss, when present, is hydrogen and each of .R^JW, and R⁰'^;t\ when present, is merayt.

hi a further aspect, R^J'^:\ when present, is hydrogen and each of R'^K>, R'^,{, and R^;i2w, when present, is mdependently selected from C1-C3 alkyl, C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl. In a still further aspect, R‘^>0\ when present, is hydrogen and each of R’°, R^>!, and R⁵^ when present, is independently selected from C1-C3 monohaloalkyl, and C1-C3 polyhaloalkyl. In yet a further aspect, R⁰⁰⁸, when present, is hydrogen and each of R’0^, R^;(i, and R'^ub, when present, is independently selected from -~CH?F, -CH?CI,

-CH₂CH₂F, -CH₂CH₂Ci, -CHF₂, -CH₂€H.F₂, -C.P₃, -CH₂CF₅, -CHC1₂, -CH₂CHCl₂,

-CC.U, and -CFFCCR. In an even further aspect, R:’²³, when present, is hydrogen and each of R-'°, R-”, and R.'^ut>, when present, is independently selected from -CMP*, --CHjCHFj,

-CFj, -CH2CF3, -CHt% -CH₂CHt% -CCh, and -CHbCCU. In a still further aspect, R'""’, when present, is hydrogen and each of R'^,e, R^-'*, and R^;,*^b, when present, is independently selected from -C’F_;s, -CFFCF;, -CCU, and -CH2CCI3.

In a further aspect, R"³, when present, is hydrogen and each ofR*'⁰, R'^>J, and R"^b, when present, is C1.-C3 alkyl. In a still further aspect, R'^2a, when present, is hydrogen and each ofR'⁵⁰, R”, and R'¹ⁱ'^l\ when present, is selected from methyl and ethyl. In yet a further aspect, R'^lj3, when present, is hydrogen and each of R:^>0, R^,!, and R"^Ub, when present, is methyl

In a further aspect, each of R/^fl and R^j!, when present, is hydrogen and each of R^,ia and R''^, when present, is independently selected from CS-C3 alkyl CI-C3 monohaloalkyl, andCi-C3 polyhaloalkyl In a still further aspect, each of R^Kl and R:^>1, when present, is hydrogen and each ofR'^,?a and R^,3\ when present, is independently selected from C1-C3 monohaloalkyl, and C.1 -C3 polyhaloalkyl In yet a further aspect, each of R‘^,u and R'^J,i, when present, is hydrogen and each of R^J38 and R^;(2b, when present, is independently selected from-CH₂F, -CFfrCl, -CH₂CH₂F, --CFfrCHjCk -CRF₂,

-O-kOWi, ~CF₃.-CH₂CF₂, -CHCl, ~€H₂CHCl, ~€Ch, and-CHjCCfe. In an even further aspect, each of R''⁵ and R:^>!, when present, is hydrogen and each of R^Jis and R'"^>b, when present, is independently selected from -CHF₂, -CFbCHF?, -CF₃, -CHjCF?,

-CHClj, -CH2CHCI3, -CCi₃, and -CHyCCk In a still further aspect, each of R^w and R³¹, when present, is hydrogen and each of R^J2:i and R^>ab, when present is independently selected from ~CF₂, ~~CH₂CF₅, -CCS5, and -CI-frCCR.

la a further aspect, each of R^>0 and R³\ when present, is hydrogen and each of R,^aa and R'^,a’, when present, is CI-C3 alkyl lit a still further aspect, each of R’^Wi arid R”, when present, is hydrogen and each of.R'^va and R’^v'\ when present, is independently selected from methyl and ethyl. In yet a further aspect, each of R^ and R'°, when present, is hydrogen and each of R'~^a and R^aai>, when present, is methyl

In a further aspect, each of R'°. R^!>, and R^aaS is hydrogen and R^’is selected from C1 -C3> alkyl, C1-C3 monohaloalkyl and C1-C3 polyhaloalkyl In a still further aspect, each of R''°, R³*, and R'"^:ilis hydrogen and R³²¹’ is selected from C1-C3 monohaloalkyl, and Ci~C3 polyhaioaikyl. to yet a Further aspect, each ofR'⁵¹’, R"'\ and R*'²* is hydrogen and R"* is selected from -CH?F, “CBjCl. -CH₂CH_?F, -CHjCffeCl ~CHF₂, ~CH_?CHF_?, -CF.*,

-CH₂CF₂, -CHCl₂, -CH₂CHCl₂, -CC*u and -CH₂C(%. In an even further aspect, each ofR^JU, R'\ and R''¹'¹ is hydrogen and Vc^yii> is selected from -CHF₂, --CH2CHF2, -CF;;,

-CH2_CFj, -Odd2, -CHfeCHd* “CC1₃, and -CI-FCCk In a still further aspect, each of R''*¹, R'^>{, and R^yJ'^! is hydrogen and R^Vinis selected from-CF?_S -CH₂CF₃, -CCb, and

-CH2CCI3.

In a further aspect, each of R'°, R⁴*, and R'^u* is hydrogen and R'^'is CI-C3 alkyl. In a still further aspect, each ofR'^,f>, R"'\ and .R'’⁴'⁴ is hydrogen and is selected from methyl and ethyl. In yet a further aspect, each of R^j0, R”\ and R"® is hydrogen and R' is methyl

(11) R⁴⁴and R^M Groups

In one aspect, each of R" and R⁴⁴, when present, is independently selected from

-O',-OR⁴⁵, C1-C3 alkyl, CI-C3 monohaloaikyi, C1-C3 polyhaioaikyl, and -NR^MaR^m In a further aspect, each ofR" and R'^a, when present, is .independently selected from -0",

-OR^,s, and -NR^?<lii.R'^,<>b. in a still further aspect, each ofR³'' and R'l when present, is independently selected from-OR'' and -NR’^<"^,R⁴"^t\ In yet a further aspect, each ofR" and R^j4, when present, Is -OR". In an even further aspect, each ofR^-'” and R'*⁴, when present, is -NR^R**

In a further aspect, each ofR”'⁴ and R^:'\ when present, is independently selected from CI-C3 alkyl, CI-C3 monohaloaikyi, and C1-C3 polyhaioaikyl. In a still further aspect, each ofR" and R^a4, when present, is independently selected from methyl, ethyl, -CH₂F,

-CHjCl, -CH₂CHj'F, “CH2CH2CI, -CHF₂, -€H₂CHF₂, -CF₃, ····0) ·0 -CHClj,

-CH₂€HC1₂, -CCIj, and -CHjCClj. In. yet a further aspect each ofR³⁴ and R³⁴, when present, is independently selected from methyl -C.H₂F, -C.H.₂C1, -C.HF_2> -C.P3, -CHCF,

-CGI, and -€H₂CC1₂.

(1.2) R^4S AND Groups

In one aspect, each ofR"'⁵, and when present, is independently selected from hydrogen, C.1-C3 alkyl, C1-C3 monohaloaikyi, a«dCl~C3 polyhaioaikyl. In a further aspect, each ofR”', R'^,Ca, and R"^a, when present, is hydrogen.

1« a further aspect, each of R'\ R'^ki\ and R^-'**, when present, is independently selected from hydrogen, C1-C3 monohaloalkyi, and C.I-C3 polyhaloalkyl. In a still further aspect, each of R'¹ \ R^>h\ and R’”*, when present, is independently selected from hydrogen,

-CHiF, -CHiCI, “CH2CH2F, -CH>CH._;a, ~€HF₂, --CH>CHF>, -CF₃, -CH₂CF₃, ~-€BCF, -CH₂CHCl₂, -CC1;;, and ~€H₂CCh, in yet a further aspect, each of R³⁵, R*\ and R'⁶\ when present, is independently selected from hydrogen, -C'H-_;F, -CFFCI,

-C.HF-?,-CFj, -CHCI', and-CCF.

In a further aspect, each of R'\ R'^ksl, and R^k'“, when present, is independently selected from hydrogen and C1.-C3 alkyl. In a still further aspect, each ofR^s3, R^>6a, and R/^,fe, when present, is independently selected from hydrogen, methyl and ethyl. In yet a further aspect, each of R‘^!‘\ R’*\ and R^kA, when present, is independently selected from hydrogen and methyl.

In a further aspect, R’“ is hydrogen and each ofR''*”* and R³** is independently selected from CI-C3 alkyl, CI-C3 monohaloalkyi, and C.1-C3 polyhaloalkyl. in a still further aspect, R'^b is hydrogen and each of R^k>a and R'*^b is independently selected from CI C3 alkyl, C1-C3 monohaloalkyi, and CI-C3 polyhaloalkyl. In yet a further aspect, R^x> is hydrogen and each ofR'¹*⁴ and R"^ki' is independently selected from methyl, ethyl, -CMjF,

-CIFCI, -ClFCHjF, -CHjCI-bCl, -~CHF₂, -CIFaiF,. -CF_S, ~CH₂CF₂, -Clith,

-CH2CHCI2, -CC1.}, and -CFFCCl;;. In an even further aspect, R’^>5 is hydrogen and each of R3^*8 and R³** is independently selected front methyl, -CFFF, -CFFCl, -CRFj, -CFj,

-CHCJj, -CC!,,

In a further aspect, R^;,<,a is hydrogen and each of R³’ and R'^><y> is independently selected from Cl -C3 alkyl, C.I-C3 monohaloalkyi, and C1-C3 polyhaloalkyl. In a still further aspect, R^j6a is hydrogen and each of R’⁵ and R³'* is independently selected from Cl-C3 alkyl, C1-C3 monohaloalkyi, andCl*C3 polyhaloalkyl. In yet a further aspect, R‘^k’^ais hydrogen and each ofR³⁵ and R³** is independently selected from methyl, ethyl, ~CH₂F, ™CH₂Cl. ™CH₂CH₂F, ~€H₂CH₂CI, ™CHF₂, ~€H₂CHF₂, ~CF_3s ~~CH₂CFj, -CHCF, ~-CH₂.CHCl₂, -CCI3, and-CHsCCU. In an even further aspect, R*""⁴ is hydrogen and each of R" ' and R^kk> is independently selected from methyl, -CFFF, -CFFCl, -CHF₂, -CF₃,

-CHClj, and “CCI3.

1« a further aspect, each of Rr'^sand R'^,6a is hydrogen and R'^a> is selected from Ci-C3 alkyl, Ci-C3 monohaloalkyl, and C1-C3 polyhaioaikyl. In a still further aspect, each of R'¹'' and R"^fe i$ hydrogen and R^><A is selected from methyl, ethyl, -OFF, -CH?Cl,

-CHiCHjF, -OfcCtfcCi, ~CHF₂, -CH>CHF>, ~CF.:. -CI-bCFj,~~CHCh.“OFCHCh.

-CClj, and-CHsCCIj. In yet a further aspect, each of R:’⁵ and R^K,a is hydrogen and R'^,6i> is selected from methyl, -OFF, -CH,C1, -CFLF₂, -CT_3s -CHCIj, and -CCl₃.

{13) R^4,), R⁴’, and R⁴² Groups

in one aspect, each of R'^w, R^+!, R^4a\ and R^42b, when present, is independently selected from hydrogen, CI-C3 alkyl. Cl -C3 monohaloalkyl, and C1-C3 polyhaioaikyl In a further aspect, each of R⁴⁰, R^4:, R⁴'^!i!, and when present, is hydrogen.

In a further aspect, each of R⁴⁰, R^4!. R^42a, and R*⁴\ when present. Is independently selected from hydrogen, C1-C3 monohaloalkyl, and CJ-C3 polyhaioaikyl In a still further aspect, each ofR⁴⁰, R*\ R^4J“, and R^4a', when present, is independently selected from hydrogen, --OFF. -CFE₂Cl -CH₃CH₂F_t -CHjCftCl, -CHF₂, -CH₂CHF₂,

--O':. -CH₂CF₂, ····Π1Π:-. -CH₂CH€I₂,-CC!_Jt and-OFCCk In yet a fitrther aspect, each ofR⁴⁰, R⁴', R^42s, and R^4ai>, when present, is independently selected from hydrogen, ™CHF₂, ™CH₂CMF₂, -CF₃, -CHj.CF.5, -CHCij, ~CH₂CHCk -eCij, and -O-fcCXk In an even further aspect each of R'"'¹, R*\ ΧΧ and R‘^iih, when present, is independently selected from hydrogen, -CF_?> -CH₂CF₃, -CCi₃, and -CkFCCfr.

In a further aspect, each of R⁴²', R⁴', R^42a, and R⁴X when present, is independently selected from hydrogen and C i~C3 alkyl. In a still further aspect, each of R⁴⁰, R⁴ⁱ, R⁴ⁱ\ and R^4Jo, when present, is independently selected front hydrogen, methyl, and ethyl. In yet a further aspect, each ofR"^w, R⁴\ R"^,?\ and R⁴²\ when present, is independently selected from hydrogen and methyl.

in a further aspect, R⁴⁰, when present, is hydrogen and each of R"^l!, R⁴"^:a, and R^4?‘\ when present, is independently selected from C1.-C3 alkyl, C1.-C3 monohaloalkyl, and CI-C3 polyhaioaikyl. In a still further aspect, R“'^J, when present, is hydrogen and each of R^4f, R⁴"“, and R⁴'^b, when present, is independently selected from C1-C3 monohaloalkyl, and Cl-03 polyhaioaikyl. in yet a fitrther aspect, R'^w, when present, is hydrogen and cadi of R^4!, R⁴k and R^4a>, when present, is independently selected from -OFF, -~QFQ,

-ClfcCHjF, ~CH₂CH₂C1₅ -CHF>, -CH2CHF2, ™CF₃, -CMXF₃> -CBCF, -CBCBCF,

-CCls, and -CHjCCU. In an even further aspect;, R*°, when present is hydrogen and each of R⁴ⁱ, R⁴⁴³, and R⁴²*, when present, is independently selected from -CHFj, -CHjCHFj,

-CFj, -CH2CF3, -CHCfe, -CH₂CHC1_2> “CCIj, and -CffeCCU. In a still further aspect, R⁴⁰, when present, is hydrogen and each of R⁴', R⁴²'¹, and R⁴**, when present, is independently selected from -CF?, -CHjCF*, -CCU, and -CH3CCI3.

In a further aspect, R⁴⁰, when present is hydrogen and each of R⁴’, R⁴^, and R^44b, when present, is C1-C3 alkyl. In a still further aspect, R⁴⁰, when present, is hydrogen and each of R⁴¹, R'^!'^,J, and R^4ib, when present, is selected from methyl and ethyl. In yet a further aspect, R^4<1, when present, is hydrogen and each of R⁴ⁱ, R⁴"*, and R⁴"*¹, when present, is methyl

In a further aspect, ft^4!, when present, is hydrogen and each of R^4u, R⁴"^;a, and R^4ib, when present, is independently selected from CI-C3 alkyl, CI-C3 monohaloalkyl, and CI *C3 poiyhaioalkyl. In a still further aspect, R"¹, when present, is hydrogen and each of R⁴⁰, K^44s, and R⁴'^b, when present is independently selected from CI-C3 monohaloalkyl, and C1-C3 poiyhaioalkyl. In yet a further aspect, R^+!, when present, is hydrogen and each ofR⁴”, R⁴***, and R^4ib, when present, is independently selected from -~€H;>F, -CH₂C1,

-CH₂CH>F, -CH₂CH₂CI, -CHF_a, -CH₂CHF₂, “CFj, -ch₂cf₃, -c.h.ci_2> -ch₂chci₂, CCI3, and -CHjCCl;!. In an even further aspect, R^, when present, is hydrogen and each ofR*⁰, R^44a, and R^42t>„ when present, is independently selected from ~-CHF₂, -CHjCHFj, “CF?_, -CHjCFj, ~CHC1₂, “CH₂CHC1_2j -CCF, and -CRjCCR, In a still further aspect, R⁴ⁱ, when present, is hydrogen and each of R⁴ⁱ\ R⁴'*⁵, and R⁴"^:b, when present, is independently selected from -CFj, -€H₂CF_3> -CC1_3> and -CRjCCLf.

In a further aspect, R⁴*, when present, is hydrogen and each of R⁴'’, R⁴'^;a and R^4ab, when present, is C1-C3 alkyl. In a still further aspect, R^4!, when present, is hydrogen and each of R⁴⁰, R"*'¹, and R^4ab, when present, is selected from methyl arid ethyl. In yet a further aspect, R^4:, when present, is hydrogen and each of R⁴⁰, R⁴^, and R^4?b, when present, is methyl

In a further aspect, R⁴"'^a, when present, is hydrogen and each of R^-*⁴, R^4!„ and R^4ab when present, is independently selected from CI-C3 alkyl, C1-C3 monohaloalkyl, and CI-C3 poiyhaioalkyl. In a still further aspect, R"*'¹, when present, is hydrogen and each of R⁴⁰, R^4!, and R^4ab, when present, is independently selected from C1-C3 monohaloafkyi, and Ci~C3 polyhaioaikyl. to yet a Further aspect, R^4ia, wheu present, is hydrogen and each of R.⁴⁰, R⁴ⁱ, and R^44b, when present:, is independently selected from -CHjF,-CHjCi,

-Q-FORF, -OFCFFCl, -CMF₂, -CHjCHFj, -CFa, -CH₂CFj, -CRC1_2s -CHsCHCF,

-CClj, and-ClRCCl.?. In an even further aspect, R⁴*⁴, when present, is hydrogen and each of R⁴'^j₅ R⁴ⁱ₅ and R⁴~^b, when present, is independently selected from-CHF₂, -CH2CHF2,

-CFj, -CHjCFv, -CHClj, -CHjC HC lj, -CCI_3t and -CHjC Cl$. hi a still further aspect, R^4?a, when present, is hydrogen and each of R^4W, R^4!, and R^4?i>, when present, is independently selected from-CF;?, -ClRCF-s, -CCR, and-CIHRCCR.

in a further aspect, R⁴"'¹', when present, is hydrogen and each of R⁴⁴, R'^ft, and R4^2b, when present, is CI-C3 alkyl. In a still further aspect, R⁴⁴⁸, when present, is hydrogen and each of R'^kl, R⁴\ and R.^+8h, when present, is selected from methyl and ethyl. In yet a further aspect, R^42a, when present, is hydrogen and each, of R⁴⁰, R⁴‘, and R^4ab, when present, is methyl.

In a further aspect, each of R⁴⁰ and R⁴¹, when present, is hydrogen and each of R4^{^} and R⁺'^b, when present, is independently selected from CI-C3 alkyl, CI-C3 monohaloalkyi, and C.I-C3 polyhaioaikyl In a still further aspect, each of R^w and R⁴ⁱ, when present, is hydrogen and each of R*'⁸¹ and R^4?b, when present, is independently selected from C1-C3 monohaloalkyl, and C1-C3 polyhaioaikyl. in yet a further aspect, each of R*⁰ and R*¹, when present, is hydrogen and each of R^44a and R^4-Ji>, when present, is independently selected from -CH₂F, -CH₂Cl -CH₂CH₂F, -CH₂CH₂C1, -CH'F₂,

--CR'CRP', -CP,, -CHjCFj, “CHCF, -CHjCHCh, -α:ΐ = . aad-CH₂CC1s. in an even further aspect, each of R^4u and R⁴ⁱ, when present, is hydrogen and each of R⁴'^!a and R^43ti, when present, is independently selected from -CHF_2s -€H;jCHF;>, -CF_3> -CIljCF.?,

-CHCF, -CH2CHCF, -CCh, and -CH₂CCl₃. In a still further aspect, each of R⁴⁰ and R*\ when present, is hydrogen and each ofR*^aa and R^43b, when present, is independently selected from -CP*, -CH2CF3, -CO3, and ~CH₂CC!₃.

In a further aspect, each of R^4b and R^4!, when present, is hydrogen and each of R⁴⁴* and R⁺'^b, when present, is C1-C3 alkyl. In a still further aspect, each of R⁴⁰ and R*‘, when present, is hydrogen and each ofR⁴⁴* and R^4Jb, when present, is independently selected from, methyl and ethyl. In yet. a further aspect, each of R⁴⁰ and R⁴¹, when present, is hydrogen and each of.R^43s and R*'*, when present, is methyl.

1« a further aspect, each of R⁴⁰, R^4t, and R^44s is hydrogen and R^42h is selected from Cl-C3 alkyl, C1-C3 monohaloaikyl, ami Cl-C3 polyhaloalkyl. hi a still further aspect-, each of i\^R', R⁴⁴, and is hydrogen and Ris selected from CI-C3 monohaloaikyl, and CI-C3 poIyha.loa.lkyl. In yet a. further aspect, each ofR⁴⁰, R^4!, and R⁴'³is hydrogen and R^4if> is selected from ~€H₂F, -CH₂Ci, -CHaCTfcF, -CH₂CH₂Cl -CHF₂, -CH₂CHF₂, -CF₃,

-CHjCFj, -CHClj, -CHjCHCU, -CCl, and-Cf-frCCh. in an even further aspect, each of R⁴⁴, R⁴’, and R⁴²* is hydrogen and R^42b is selected from -CHF₂, -CBjCHF;, -CF*, CiHvCF i, -CHCl₂, -CH₂CHCl₂, -CCt;, and -CHjCClj. In a still further aspect, each of R⁴⁰, R⁴ⁱ, and R⁴²* is hydrogen and R⁴~^h is selected from -CF?, ~CH₂CFs, -CQs, and

-CHvCCk.

In a further aspect, each of R⁴⁴', R^4!, and R^'¹is hydrogen and R'^ is C1-C3 alkyl in a still further aspect, each of R^4W, R⁴\ and R^4:a is hydrogen, and R^42b is selected from methyl and ethyl. In yet a further aspect, each of R⁴¹', R⁴*, and R^ is hydrogen and R.‘^L>!> is methyl.

(14) R⁴* and R⁴⁴ Groups

In one aspect, each of R^4j and R⁴⁴, when present, is independently selected from

-O , -OR¹⁴, C1-C3 alkyl, C1-C3 monohaloaikyl C1-C3 polyhaloalkyl and -NR^46aR^4w*. In a further aspect, each of R⁴' and R⁴⁴, when present, is independently selected from -Q\

-OR⁴", and --NR'^todR^4!!f!, In a still further aspect, each of R⁴³ and R.⁴⁴, when present, is independently selected from -OR⁴⁵ and HNR⁴⁰*!!.'**. In yet a further aspect, each of R^a' and R⁴⁴, when present, is -OR⁴⁵. In an even further aspect, each of R⁴' and R*⁴, when present, is -NR^R⁴⁶*

la a further aspect, each of R^4> and R⁴⁴, when present, is independently selected from C1.-C3 alkyl, C1.-C3 monohaloaikyl, and C1-C3 polyhaloalkyl In a still further aspect, each of R^4j and R⁴\ when present, is independently selected from methyl, ethyl, -CH₂F,

-CHjCl, -CHjCHjF, ~CB?CB_?C1, -CBFj, ~CB?CHF?, -CF_S, -ΠΚΤ:, -CBCb,

-CHjCHCb, -CCb, and -OfcCCU. In yet a further aspect, each of R⁴³ and R⁴⁴, when present, is independently selected from methyl, -CH;F, -CH₂.C1, -CHF₂, -CF?, -CHC1₂, ~CCI.>, and -CH2CCI3.

{15) R⁴⁵and JR*' Groups

In one aspect, each ofR⁴', R⁴⁶*, and R^4ob, when present, is independently selected from hydrogen, C1-C3 alkyl CI-C3 monohaloalkyl, andCl-C3 polyhaloalkyl. In a further aspect, each ofR⁴', R^4<,‘\ and R^44h, when present, is hydrogen.

In a further aspect, each of R'^}'\ R^4<a, and R⁴**, when present, is independently selected from hydrogen, CI-C3 monohaloalkyl, and C1-C3 polyhaloalkyl In a still further aspect, each of R⁴⁵, R^¹, and R^46b, when present, is independently selected from hydrogen,

-OFF, -™αΐ;℮1, -CFICIFF, -OfcOfcCl, -~€HF_:, -CffcCHFj, -CF₃, ~CH_;CF_3:,

-CHCls, -CHjCHClj, -CCh, and -CMjCCR. In yet a further aspect, each ofR⁴⁵,K^m, and R^46b, when present, is independently selected from hydrogen, -CffrP, -CH₂CI»

-CHP_2s -CF₃, -CHC1₂, and -CCI₃.

In a further aspect, each of R⁴⁵, R^4,!a, and R^4<n>, when present, is independently selected from hydrogen and C1-C3 alkyl in a still further aspect, each of R⁴\ R^4<>\ and R^¹’, when present, is independently selected from hydrogen, methyl and ethyl, in yet a further aspect, each of 11*1 R⁴⁰⁴, and R^4<*, when present, is independently selected from hydrogen and methyl

In a further aspect, R^4s is hydrogen and each of R^4fe and R⁴^ is independently selected from CI-C3 alkyl, C1-C3 monohaloalkyl and C.1-C3 polyhaloalkyl In a still further aspect, R⁴⁵ is hydrogen and each ofR⁴'¹⁴ and R^46b is independently selected from Cl* €3 alkyl, CI-C3 monohaloalkyl, and C1-C3 polyhaloalkyl. In yet a further aspect, R^4> is hydrogen and each of.R^4<* and R^’ is independently selected from methyl ethyl, -CliF, ~CH₂Cl ~€H₂CH₂F, -CHjCHjCI, ~CHF₂, -CH₂CHF_2> ~€F,_:, -ClIjCF;, ~CHCl, “CHjCHClj., -CCR, and-CHjCCii. In. an even further aspect, R⁴” is hydrogen and each, of R^4& and R^4(Ui is independently selected from methyl, ~CH₂F, -CH.Cl, -CHF₂, -CP₃, CHCl, -CCR,

In a further aspect, R^4<>ais hydrogen and each ofR⁴⁵ and R^4ob is independently selected from Cl -C3 alkyl, C.I-C3 monohaloalkyl and CI-C3 polyhaloalkyl. In a still further aspect, R⁴⁴'⁵ is hydrogen and each ofR'’*' and R^4ob is independently selected from Cl-C3 alkyl, C1-C3 monohaloalkyl and Cl-C3 polyhaloalkyl. in yet a further aspect, R⁴** is hydrogen and each of R"⁵ and R⁴^ is independently selected from methyl, ethyl, -CH₂F,

-CB₂Cl, -CFFCFIF, ~CB>CH₂Cl, -CBF_2s ~CB>CHF>, ~CF₂, ™CH₂CF₂, -CPICl,

-C.H2CHCI2, -CCb, and -CH?CCij. In an even further aspect;, R*⁶* is hydrogen and each of R⁴⁵ and K^m is independently selected from methyl, ~~CH₂F, ~~CH₂C1, -CHF₃, ~CF_S,

-CHC1₃, and-CCk.

hi a further aspect, each of R⁴⁵ and R"⁶'* is hydrogen and R⁴** is selected from CI-C3 alkyl, C1-C3 monohaioalkyi, and Ci-C.3 polyhaloaSkyl. In a still further aspect each of R** and R*⁶* is hydrogen and R^4<* is selected from methyl, ethyl, -~CH₂F, "ChfrCI, ~~CH₂CH₂F, -CI-bCHiCL -CHFj, -CkbCHF,, -CFj, ~~C%CF₃, -CHGb, ~CH₂CHCl>,

-CCls, andCH₂CCb. In yet a further aspect, each of R⁴’ and R‘^>4a is hydrogen and R"^K,b is selected from methyl, -CH₂F, ~CH₂C1, -CHF₂, -CF*, -CllCk, and ~€Ch.

(16) X

In one aspect, s is an integer greater than I. In another aspect, χ is an integer greater than 10, In a further aspect, χ is an integer greater than 100,

(17) Counterions

hi certain embodiments, the polymer further comprises an acceptable counterion. lh one embodiment, the counterion is selected from iodide, bromide, chloride, fluoride, sulfate, hydrogen sulfate, perchlorate, nitrate, carbonate, hydrogen carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, acetate, and formate.

In one aspect, the polymer is formed by polymerizing a compound having a structure:

Η

Η

Η

1

Η

Η

OH

Η

In one aspect, the polymer has a structure represented by a formula:

In a further aspect, the membrane is cast onto a support structure. In a still further aspect, the support structure is a nonwoven support fabric, in a preferred embodiment, the support structure is a nonwoven polyester fabric,

3. U 1..TR A T11.TR A TION MEMBRANES

In various aspects, the membranes of the invention are uitrafiltration membranes. Examples of high-performance synthetic polymers commonly used in the formation of uitrafiltration membranes include polysulfone, poiyethersuifone, and polyacrylonitrile.

One advantage of uitrafiltration membranes comprising the disclosed polymers involves the potential to impart passive fouling resistance to the support layer. Passive fouling resistance, sometimes referred to as ‘‘passivation,⁵' describes modification of a surface to reduce surface reactivity and promote hydrophilicity. Passive fouling resistance can prevent unwanted deposition of dissolved, colloidal or microbial matter on the membrane surface, which tends to foul the membrane and negatively influence fins and rejection.

The present invention provides a ne w class of uitrafiltration membranes with improved hydrophilicity and chlorine-resistance o ver conventional uitrafiltration membranes. Development of more efficient, more selecti ve membranes with tunable surface properties holds great promise for advanced protein separation, dialysis, water filtration, and other macro molecular separations.

4. Ν A NO FH ,TRA1 ION MEMBRANES

In various aspects, the membranes of the invention are nanofiltration membranes. Typical high-performance synthetic polymers commonly used in the formation of .oanofiltratlon membranes include poiysulfone, polyethersulfone, and polyacrylonitrile.

S These iianofiltration membranes can he prepared, for example, by non-solvent induced phase separation (NIPS).

Another advantage of nanofiltration membranes comprising the disclosed polymers involves the potential to impart passive fouling resistance to the support layer, Passi ve fouling resistance, sometimes referred to as “passivation,” describes modification to of a. surface to reduce surface reactivity and promote hydrophilicity. Passive fouling resistance can prevent unwanted deposition of dissolved, colloidal, or microbial matter on the membrane surface, which tends to foul the membrane and negatively influence flux and rejection.

{S improved hydrophilicity and chlorine-resistance over conventional nanofiitration membranes. Development of more efficient, more selective membranes with tunable surface properties holds great promise for advanced protein separation, dialysis, water filtration, and other macro molecular separations.

5. Osmosis Membranes

20 In various aspects, the membranes of the invention can he osmosis membranes, for example, forward osmosis membranes, reverse osmosis membranes, or pressure retarded osmosis membranes without thin film coating. Among particularly useful membranes for osmosis applications are those in which the discriminating layer is a polyamide.

25 Composite polyamide membranes are typically prepared by coating a porous support with a poly functional amine monomer, most commonly coated from an aqueous solution. Although water is a preferred solvent, non-aqueous solvents can be utilized, such as acetonitrile and dimethylformamide (DMF). A polyfunctiona.1 acyl halide monomer (also referred to as acid halide) is subsequently coated on the support, typically coated first on the 30 porous support followed by the acyl halide solution. Although one or both of the polyfunctionai amine and acyl halide can be applied to the porous support From a solution, they can alternati vely be applied by other means such as by vapor deposition, or heat.

In a further aspect, the membranes of the invention can further comprise a thin film polymerized onto a surface of the membrane, and the membrane is an osmosis membrane. In a still further aspect, the osmosis membrane is selected from a reverse osmosis membrane and a forward osmosis membrane.

6. Film

In various aspects, the membranes of the invention further comprise a thin film polymerized onto a surface of the membrane. The thin film can be a semi-permeable polymer matrix, e.g. with a three-dimensional polymer network, substantially permeable to water and substantially impermeable to solutes. For example, the polymer network can be a cross-linked polymer formed from reaction of at least one polyfunctional monomer with a difunctional or polyfunctional monomer.

The polymer matrix film can be a three-dimensional polymer network such as an aliphatic or aromatic polyamide, aromatic polyhydrazide, poly-bensimidazolone, polyepiamine/amide, polycpiaxuinc/urca, a polyester, or a polyimide or a copolymer thereof or a mixture thereof. Preferably, the polymer matrix film can be formed by an interfacial polymerization reaction or can be cross-linked subsequent to polymerization.

Tire polymer matrix film can be an aromatic or non-aromatic polyamide such as residues of a phthaloyl (e.g., isophthaloyl or terephthaioyl) halide, a trimesyl halide, or a mixture thereof, in another example, the polyamide can be residues of dtaminobeuzene, tmminohenzene, polyetherimine, p iperazine or poly-piperazine or residues of a trimesoyl halide and residues of a diaminobenzene. The film can also be residues of trimesoyl chloride and .fw-phenylenediamme. Further, the film can be the reaction product of trimesoyl chloride and w-phenylenediamine.

The polymer matrix film can have a thickness of from about i nm to about 1000 nm. For example, the film can have a thickness of from about 10 nm to about 1000 nm, from about 100 nm to about 1000 nm, from about i nm to about 500 nm, from about 10 nm to about 500 nm, from: about 50 nm to about 500 nm, from about 50 nm to about 200 run, from about- 50 ma to about 250 nm, from about 50 nra to about 300 am, or from about 200 nra to about 300 nm.

7. Properties

In various aspects, the composite filtration membranes of the invention ca n have various properties that provide the superior function of the membranes, including improved hydroplvilicity, improved resistance to chlorine, excellent permeability, and improved salt rejection. It is also understood that the membranes have other properties.

a. HvDRomiLicn υ

The hydroplvilicity of the membranes can be expressed in terms of the pure water equilibrium contact angle. The contact angles of the membranes of the invention, can be measured using a contact angle goniometer (DSAI0, KRUSS GmbH).

In various aspects, a membrane of the invention can have a pure water equilibrium contact angle of less than about 90°. In a further aspect, a membrane of the invention can have a pure water equilibrium contact angle of less than about 80°. In a still thither aspect, a membrane of the invention can have a pure wafer equilibrium contact angle of less than about 70°. In yet a further aspect, a membrane of the invention can have a pure water equilibrium contact angle of less than about 60°. In an even further aspec t, a membrane of the invention can have a pure water equilibrium contact angle of less than about 50°. in a still further aspect, a membrane of the invention can have a pure water equilibrium contact angle of less than about 40*. In yet a further aspect, a membrane of the in vention can have a pure water equilibrium contact angle of less than about. 30*. In certain embodiments, a membrane of the invention, can have a pure water equilibrium contact angle of about 20*. about 30*, about 31*, about 32*, about 33*, about 34*, about 35*, about 36*, about 37*. about 38*, about 39*, or about 40*.

b. Permeability

The permeability of the membranes can be expressed in terms of the pure water permeability. The permeability of the disclosed membranes cart be measured, for example, using a dead-end stirred cell (Slerhtech).

.Membrane permeability can be affected by, for example, the amount of polymer present. Thus, in various aspec ts, the polymer is present in an amount of about 30 wt% and the membrane Stas a pure water permeability of less than about 5.00 gfd/psi. in a further aspect, the polymer is present in an amount of about 30 wt% and the membrane has a pure water permeability of less than about 4,50 gfd/psi. In a still further aspect, the polymer is present in an amount of about 30 wt% and the membrane has a pure water permeability of less than about 4.00 gfd/psi. In yet a further aspect, the polymer is present in an amount of about 30 wt% and the membrane has a pure wafer permeability of less than about 3.50 gfd/psi. In certain embodiments, the polymer is present in an amount of about 30 wt% and the membrane has a pure water permeability of about 3,0 gfd/psi, about. 3.1 gfd/psi, about 3.2 gfd/psi, about 3.3 gfd/psi, about 3.4 gfd/psi, about 3.5 gfd/psi, about. 3.6 gfd/psi, about 3.7 gfd/psi, about 3.8 gfd/psi, about 3.9 gfd/psi, or about 4.0 gfd/psi.

c. Rejection

The rejection of the membranes can be expressed in terms of bovine serum albumin (BSA) rejection. The salt rejection of the disclosed membranes can be measured, for example, using a dead-end stirred cell (Sterlitech).

The salt -rejection of the membranes can be affected by, for example, the amount of polymer present. Thus, in various aspects, the polymer is present in an amount of about 30 wt% and the membrane has a 8SA rejection of at least about 50%. in a further aspect, the polymer is present in an amount of about 30 wt% and the membrane has a BSA rejection of at least about 55%. In a still further aspect, the polymer is present in an amount of about. 30 wt% and the membrane has a BSA rejection of at least about 60%. In yet a further aspect, the polymer is present in an amount of about 30 wt.% and the membrane has a BSA rejection of at least about 65%, hi an even further aspect, the polymer is present in an amoun t of about 30 wt% and the membrane has a BSA rejection of at least about 70%.

In certain embodi ments, the polymer is present in an amount of about 30 wt% and the membrane has a BSA rejection of about. 60%, about 62%, about. 64%, about 66%, about.

68%, about 70%, about 72%, about 74%, about 76%, about 78%, or about 80%.

C. Methods tor Making Filtration Membranes

In one aspect, the invention relates to a method of making a filtration membrane, the method comprising the step of providing a poly mer formed by poly merizing a compound having a structure -represented by a formula;

,,, I Η '[ ,R"° R13 R^JC ,

" ' ^ R^!dA AR^{2a r2&} i ! 'T yyn^R

R¹

wherein η is selected from 1,2, and 3; wherein each of R^1:\ R^fb, R^u, and R^ie is independently selected from hydrogen, halogen, -CM, -SR*¹, -GR'h -NR^R"*,

-ΝR^JJ:iR.^M\ -S0₂R^?"\ -(COIR³⁴, and C1-C3 alkyl substituted with 0, 1, 2, or 3 groups selected from halogen, -CM, -SR²⁰, -OR^2!,-NR²²⁴R²²ⁱ\ -SOjR²³, and-COOJR²⁴;

wherein each of R²® and R^2h is independently selected from hydrogen, halogen, -CM,

-SR²⁰, -OR³⁵, -NR^32aR^32l>, -NR^R^ir, -S0₂R³³, -(C=0)R^?4, and Cl -C3 alkyl substituted with 0, 1,2, or 3 groups selected front halogen, -CN, - SR"’⁰, -OR^,!,

-NR'^R'’²⁰, - SO;;R''\ and~((>0)R'f wherein each ofR^JS, R'\ and R'" is independently selected from hydrogen, halogen, -CM, -SR⁴⁰, -OR⁴', -NR^4?i,R^42l>, -NR^42aR^42l>H\

-S0₂R⁴'\ and -(COIR⁴⁴; wherein at least one ofR^?3, R²\ R^3a« R³⁰, and R³° is not hydrogen; wherein each ofR²⁰, R^2t, R^22a, R^22b, R^:}0, R^?f, R³²\ R^32b, R⁴⁰, R⁴⁵, R^42a, and R⁴²*, when present, is independently selected from hydrogen, CI-C3 alkyl, CI-C3 nionohaloalkyi, and C1-C3 polyhaloalkyl; wherein each of R²"¹ and R*⁴, when present, is independently selected from -O', -OR²⁵, C1-C3 alkyl C1-C3 monohaloaikyl, C1-C3 polyhaloalkyl, and -NR^R²*⁴*; wherein each of R²\ R^2ts’, and R***, when present, is independently selected from hydrogen, CI-C3 alkyl, CI-C3 monohaloaikyl, and CI-C3 polyhaloalkyl; wherein each ofR⁴³ and R³⁴, when present, is independently selected from

-O',-OR³⁵, C1-C3 alkyl, C1-C3 monohaloaikyl, C1-C3 polyhaloalkyl and -NR'^l<,itR'^,<k>;

wherein each of R”, R'’⁶⁴, and R²⁶⁰, when present, is independently selected from hydrogen, C1 -€3 alkyl, C1-C3 monohaloaikyl, and Ci-C3 polyhaloalkyl; wherein each of R^4-’ and R⁴⁴, when present, is independently selected from -0", -OR⁴⁵, CI-C3 alkyl, CI-C3 monohaloaikyl, C1-C3 polyhaloalkyl, and -NR^R⁴**; and wherein each of R⁴\ R^4<>a, and R.⁴⁴*, when present is selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and Cl-C3 poiyhaloalkyl; and casting a solution or a suspension of die polymer.

In one aspect, the inven tion relates to a method of making a filtration membrane, die method comprising the step of pro viding a polymer comprising a structure represented by a. formula:

wherein each Ζ is independently selected from hydrogen and R"^a ; wherein η is an integer selected from 1,2, and 3; wherein ρ is independently 0, 0.5, or i; wherein q is independently 0, 0.5, or i; wherein, for each χ, ρ -f q == j ; wherein each of ft¹**, R'^b, R^!£, and 1is independently selected from hydrogen, halogen, -CN, -SR²⁰, -OR' ’, -NR^R'²⁰,

-NR^??aR^22l>H\ -SQ₂R^B, -<O==0)R²⁴, and CI-C3 alkyl substituted with 0,1, 2, or 3 groups selected from halogen, -CN, -SR¹⁰, -OR^?2 -NR^;!BR^m, -SOjR²³, and-{O0)R²⁴;

wherein each of R²³ and .R.²⁴ is independently selected from hydrogen, halogen, -CN,

-SR³⁰, -OR^?i, -NR^;2aR^?B -NR^R'^H"; -$0;?R^B -(OO)R³⁴, and C1-C3 alkyl isubstituted with 0, 1,2, or 3 groups selected from halogen, -CN, -SR*’, -OR^>f,

-NR^R’²⁰, -SOeR’C and-(C-OjR³⁴; wherein each of R’^a, R'^,b, and R³ⁱ is independently selected from hydrogen, halogen, -CN, -SR⁴⁰, -OR⁴\ -NR^4BR^42h, -NR^42aR^42bH^<-,

-SOjR⁴⁵, and -{OQ)R⁴⁴; wherein each of R^J0, R²‘, R³²*, R^JJb, R³⁰, R^3!, R^3B R²²\ R⁴⁰, R⁴*, R⁴²*, and R⁴'^b, when present, is independently selected from hydrogen, Cl-C3 alkyl, CI-C3 monohaloalkyl, and C1-C3 poiyhaloalkyl; wherein each ofRfr* and R'⁴, when present, is independently selected from-O’,-OR"⁵, CI-C3 alkyl, C1.-C3 monohaloalkyl, C1-C3 poiyhaloalkyl, and -NR^R^'*; wherein each of R*\ R'⁵'¹*, and R²"2 when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, andCi-C3 poiyhaloalkyl; wherein each of R³' and R^>4, when present, is independently selected from

-0‘, -OR³⁵, CI-C3 alkyl,Cl-C3 monohaloalkyl,C1-C3 poiyhaloalkyl, and-NR^R⁵⁶⁰;

wherein each of R.R:’⁶®, and when present, is independently selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, and C1-C3 poiyhaloalkyl; wherein each of R⁴*' and R⁴\ when present is independently selected from-~0‘,-~OR⁴\ C1-C3 alkyl, C1-C3 monohaloalkyl, C1-C3 poiyhaloalkyl, and -NR'^R⁴⁶''; wherein each of R⁴', R^4(,J, and R^4<,t‘, when present, is selected from hydrogen, C1-C3 alkyl, C1-C3 monohaloalkyl, andC.l-C3 poiyhaloalkyl; and wherein at least one Ζ is a structure represented by a formula: