RELATED APPLICATIONS

fliidl I This application claims the benefit of U.S. Provisional Application No. 62/556,875, filed on September 11, 2017. The entire teachings of that application are incorporated herein by reference.

BACKGROUND OF THE INVENTION

(0002} The high catalytic activity of metalloenzymes inspires the design of synthetic polymers as reusable metal-supporting catalysts in aqueous systems. Metalloenzyme-inspired catalysts have the potential to serve as industrially relevant and sustainable catalytic systems. However, new catalysts are still needed.

SUMMARY OF THE INVENTION

(00031 I ^{n a} first aspect, the present disclosure provides polymers comprising at least one repeat unit represented by any one of structural formulas I or II:

wherein the values and example values of the variables are defined herein.

i0fl04| In a second aspect, the present disclosure provides polymer-palladium complexes comprising palladium and a polymer comprising at least one repeat unit represented by any one of structural formulas I or II.

{0005J In a third aspect, the present disclosure provides methods of catalyzing a hydrogenation reaction, comprising reducing a double or triple carbon-carbon bond with molecular hydrogen in the presence of the polymer-palladium complex of any one of the first or second aspects.

0i06J In a fourth aspect, the present disclosure provides methods of catalyzing a Suzuki or Heck coupling reaction, comprising forming a carbon-carbon bond in the presence of the polymer-palladium complex of any one of the first or second aspects. DETAILED DESCRIPTION OF THE DRAWINGS

(0007} FIG. 1A is a plot representing X-ray photoelectron spectroscopy (XPS) spectrum of (NH ₄ ) ₂ PdCl ₄ @Poly(«¾AO).

|β§0&| FIG. IB is a high-resolution transmission electron microscope (HRTEM) image of (NH ₄ ) ₂ PdCl ₄ @Poly(«¾AO).

10109} FIG. 1C is a Scanning Electron Microscope/Energy-Dispersive X-Ray spectroscopy (SEM/EDX) image of (NH ₄ ) ₂ PdCl ₄ @Poly(«¾AO), with CI mapping.

fOiittj FIG. ID is a SEM/EDX image of (NH ₄ ) ₂ PdCl ₄ @Poly(«¾AO), with Pd mapping.

[0011 j FIG. 2 is a plot of the yield of the hydrogenation of styrene using a catalyst described herein as a function of polymer hydrophobicity.

DETAILED DESCRD7TION OF THE INVENTION

{0012} In a first embodiment, the present disclosure provides polymers comprising at least one repeat unit represented by any one of structural formulas I or II:

The values and example values of the variable sin structural formulas (I) and (II) of the first embodiment are as defined below:

X ¹¹ , X ¹² , X ²¹ , and X ²² , each independently, are -0-, -S-, or -(NR ⁷ )-;

W ¹ is -O- or -S-, or when ring A ¹¹ is phenylene, then W ¹ is -CH=;

W ² is -O- or -S-, or when ring A ²¹ is phenylene, then W ² is -CH=;

Y ¹ , Y ² , Y ³ , and Y ⁴ , each independently, are CH or N, provided that at least one of Y ¹ and Y ² , and separately, at least one of Y ³ and Y ⁴ , is N;

ring A ¹¹ is phendiyl, furan-2,5-diyl, or thiophen-2,5-diyl, and each carbon atom of ring A ¹¹ is optionally substituted with R ¹¹ ;

ring A ¹² is pyridindiyl or pyrimidindiyl, and each carbon atom of ring A ¹² is optionally substituted with R ¹² ; ring A ²¹ is phendiyl, furan-2,5-diyl, or thiophen-2,5-diyl, and each carbon atom of ring A ²¹ is optionally substituted with R ²¹ ;

each carbon atom of ring A ²² is optionally substituted with R ²² ;

each carbon atom of ring A ²³ is optionally substituted with R ²³ ;

each carbon atom of ring A ²⁴ is optionally substituted with R ²⁴ ;

R ¹¹ , R ¹² , R ²¹ , R ²² , R ²³ , and R ²⁴ , for each occurrence independently, are selected from R ⁶ , a C1-C20 alkyl, a C2-C20 alkenyl, a C2-C20 alkynyl, a C3-C20 cycloalkyl, a 5-20 atom heterocyclyl, a C6-C20 aryl, a 5-20 atom heteroaryl, a C1-C20 alkoxy, a C6-C20 aryloxy, a C1-C20 alkylthio, a Ce- C20 arylthio, a C1-C20 alkyl sulfone, a C6-C20 aryl sulfone, -N(R ⁸ )R ⁹ , hydroxyl, -CN, nitro, or a C1-C20 acyl, wherein any alkyl, alkenyl, alkynyl, cycloalkyl, hetrocyclyl, aryl, or heteroaryl portion of R ¹¹ , R ¹² , R ²¹ , R ²² , R ²³ , and R ²⁴ is optionally substituted at any substitutable carbon atom with the group R ⁶ ;

R ⁶ , for each occurrence independently, is COOH, SO2H, SC H, PO2H2, PO3H2, - P(0)(OR ⁴ ) ₂ , or -S(0 ₂ )(OR ⁵ );

R ⁴ and R ⁵ , for each occurrence independently, are selected from Ci-6 alkyl; and

R ⁷ , R ⁸ , and R ⁹ , for each occurrence independently, are H, a C1-C20 alkyl, a C6-C20 aryl, a 5-20 atom heteroaryl, a C1-C20 acyl, or -S(0)2-.

0i:13| In various aspects of the first embodiment, if A ¹¹ is phendiyl, then none of R ¹¹ , R ¹² , R ²¹ , R ²² , R ²³ , and R ²⁴ is substituted with the group R ⁶ .

f 8Θ.Ι 41 In further aspects of the first embodiment, if A ¹² is unsubstituted pyrimidindiyl, 2- methylthiopyrimidin-4,6-diyl, or 2-phenylpyrimidin-4,6-yl, then A ¹¹ is not methylphendiyl, n- pentylphendiyl, methoxyphendiyl, or (methoxycarbonyl)phendiyl.

[ΘΘ15| In certain aspects of the first embodiment, if A ¹¹ is phendiyl, the repeat unit does not comprise a group selected from carbonate, sulfinate, sulfonate, phosphinate, or phosphonate. The remainder of the variables in formulas (I) and (II) may be selected as described herein. |β0.1<*| In a second embodiment, the present disclosure provides polymer-palladium complexes comprising palladium and a polymer comprising at least one repeat unit represented by any one of structural formulas I or II, as defined with respect to the first embodiment and various aspects thereof.

{6CU7J In certain aspects of the first and second embodiment, the repeat unit is represented by formula (I) and ring A ¹¹ is:

wherein nl is 0, 1, 2, 3, or 4. In certain aspects, nl is 1, 2, 3, or 4. The remainder of the variables in formula (I) may be selected as described herein.

f Oil 8| In certain aspects of the first and second embodiments, the repeat unit is represented by formula (I) and ring A ¹¹ is:

wherein ml is 0, 1, or 2. In certain aspects, ml is 1 or 2. The remainder of the variables in formula (I) may be selected as described herein.

0019| In certain aspects of the first and second embodiments, the repeat unit is represented by formula (I) and ring A ¹¹ is:

wherein ml is 0, 1, or 2. In certain aspects, ml is 1 or 2. The remainder of the variables in formula (I) may be selected as described herein.

|0@20| In certain aspects of the first and second embodiment, the repeat unit is represented by formula (I) and ring A ¹² is:

wherein nl is 0, 1, or 2. In certain aspects, nl is 1 or 2. The remainder of the variables in formula (I) may be selected as described herein.

| ^' 021| In certain aspects of the first and second embodiment, the repeat unit is represented by formula (I) and ring A ¹² is:

wherein nl is 0, 1, 2, or 3. In certain aspects, nl is 1, 2, or 3. The remainder of the variables in formula (I) may be selected as described herein.

6i22| In certain aspects of the first and second embodiment, the repeat unit is represented by formula (I) and ring A ¹² is:

wherein nl is 0, 1, 2, or 3. In certain aspects, nl is 1, 2, or 3. The remainder of the variables in formula (I) may be selected as described herein.

f#§23) In certain aspects of the first and second embodiments, the repeat unit is represented by formula (I) and ring A ¹² is:

wherein nl is 0, 1, 2, or 3. In certain aspects, nl is 1, 2, or 3. The remainder of the variables in formula (I) may be selected as described herein.

{0824} In certain aspects of the first and second embodiment, the repeat unit is represented by formula (II) and ring A ²¹ is:

wherein m2 is 0, 1, 2, 3, or 4. In certain aspects, m2 is 1, 2, 3, or 4. The remainder of the variables in formula (II) may be selected as described herein.

{0825 | In certain aspects of the first and second embodiments, the repeat unit is represented by formula (II) and ring A ²¹ is:

wherein m2 is 0, 1, or 2. In certain aspects, m2 is 1 or 2. The remainder of the variables in formula (II) may be selected as described herein.

0S26j In certain aspects of the first and second embodiments, the repeat unit is represented by formula (II) and ring A ²¹ is:

wherein m2 is 0, 1, or 2. In certain aspects, m2 is 1 or 2. The remainder of the variables in formula (II) may be selected as described herein.

{0027} In certain aspects of the first and second embodiments, the repeat unit is represented by formula (II) and rings A ²² , A ²³ , and A ²⁴ , taken to ether, are:

wherein n2 is 0, 1, or 2; o2 is 0, 1, or 2; and p2 is 0, 1, or 2. In certain aspects, Y ¹ is CH, Y ² is N, and n2 is 0, 1, or 2. In certain aspects, Y ¹ is N, Y ² is CH, and n2 is 0, 1, or 2. In certain aspects, Y ¹ is N, Y ² is N, and n2 is 0 or 1. In certain aspects, Y ³ is CH, Y ⁴ is N, and p2 is 0, 1, or 2. In certain aspects, Y ³ is N, Y ⁴ is CH, and p2 is 0, 1, or 2. In certain aspects, Y ³ is N, Y ⁴ is N, and p2 is 0 or 1. The remainder of the variables in formula (II) may be selected as described herein. |0§28J In certain aspects of the first and second embodiments, the repeat unit is represented by formula (la):

wherein ml is 0, 1 , 2, 3, or 4; and nl is 0, 1, or 2. The remainder of the variables in formula (la) may be selected as described herein.

|0I29| In certain aspects of the first and second aspects, the repeat unit is represented by formula (Ila):

wherein m2 is 0, 1 , 2, 3, or 4; and n2, o2, and p2, each independently, are 0, 1 , or 2. The remainder of the variables in formula (II) may be selected as described herein.

| i301 In certain aspects of the first and second embodiment, at least one carbon atom of ring A ¹¹ is substituted with R ¹¹ ; and at least one carbon atom of ring A ²¹ is substituted with R ²¹ . In certain such aspects, R ¹¹ and R ²¹ , for each occurrence independently, are selected from R ⁶ , a Ci- Ce alkyl optionally substituted with R ⁶ , a C2-C6 alkenyl optionally substituted with R ⁶ , a C2-C6 alkynyl optionally substituted with R ⁶ , a C3-C10 cycloalkyl optionally substituted with R ⁶ , a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy optionally substituted with R ⁶ , a C6-C10 aryloxy, a C1-C6 alkylthio, a C6-C10 arylthio, a C1-C10 sulfone, -N(R ⁸ )R ⁹ , a halo, hydroxyl, -CN, nitro, and a C1-C6 acyl. In certain aspects, R ¹¹ and R ²¹ for each occurrence independently, are selected from a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C10 cycloalkyl, a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy, a C6-C10 aryloxy, a C1-C6 alkylthio, a C6-C10 arylthio, a C1-C10 sulfone, -N(R ⁸ )R ⁹ , a halo, hydroxyl, -CN, nitro, and a C1-C6 acyl. In certain aspects, R ¹¹ and R ²¹ for each occurrence independently, are selected from a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C10 cycloalkyl, a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy, a Ci- Ce alkylthio, a halo, -CN, or nitro. In certain aspects, R ¹¹ and R ²¹ for each occurrence independently, are selected from a C1-C3 alkyl, phenyl, a C1-C3 alkoxy, a C1-C3 alkylthio, a halo, -CN, or nitro. In certain aspects, R ¹¹ and R ²¹ for each occurrence independently, are selected from methyl, trifluoromethyl, methoxy, methylthio, -CN, nitro, phenyl, or fluoro. In certain aspects, at least one R ¹¹ and at least one R ²¹ is C3-C20 alkyl, a C3-C20 alkenyl, a C3-C20 alkynyl, or a C3-C10 cycloalkyl. The remainder of the variables in formulas (I), (II), (la), or (Ila) may be selected as described herein.

| Θ31-| In certain aspects of the first and second embodiments, no carbon atom of ring A ¹¹ or ring A ²¹ is substituted. The remainder of the variables in formulas (I), (II), (la), or (Ila) may be selected as described herein.

{09321 In certain aspects of the first and second embodiments, at least one carbon atom of ring A ¹² is substituted with R ¹² ; and at least one carbon atom of ring A ²² is substituted with R ²² . In certain aspects, R ¹² and R ²² for each occurrence independently, are selected from R ⁶ , a C1-C6 alkyl optionally substituted with R ⁶ , a C2-C6 alkenyl optionally substituted with R ⁶ , a C2-C6 alkynyl optionally substituted with R ⁶ , a C3-C10 cycloalkyl optionally substituted with R ⁶ , a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy optionally substituted with R ⁶ , a C1-C6 alkylthio, a halo, -CN, or nitro. In certain aspects, R ¹² and R ²² for each occurrence independently, are selected from a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C10 cycloalkyl, a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy, a C1-C6 alkylthio, a halo, -CN, or nitro. In certain aspects, R ¹² and R ²² for each occurrence independently, are selected from methyl, trifluoromethyl, methoxy, methylthio, -CN, nitro, phenyl, or fluoro. In certain aspects, at least one R ¹² and at least one R ²² is a 5-10 atom heterocyclyl, a C6-C10 aryl, or a 5-10 atom heteroaryl. The remainder of the variables in formulas (I), (II), (la), or (Ila) may be selected as described herein.

{0Θ33} In certain aspects of the first and second embodiments, no carbon atom of ring A ¹² or ring A ²² is substituted. The remainder of the variables in formulas (I), (II), (la), or (Ila) may be selected as described herein.

| ^" 8 34| In certain aspects of the first and second aspects, at least one carbon atom of ring A ²³ is substituted with R ²³ . In certain aspects, R ²³ is R ⁶ , a C1-C6 alkyl optionally substituted with R ⁶ , a C2-C6 alkenyl optionally substituted with R ⁶ , a C2-C6 alkynyl optionally substituted with R ⁶ , a C3-C10 cycloalkyl optionally substituted with R ⁶ , a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a Ci-C ₆ alkoxy optionally substituted with R ⁶ , a Ci-C ₆ alkylthio, a halo, -CN, or nitro. In certain aspects, R ²³ is a Ci-C ₆ alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C10 cycloalkyl, a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy, a Ci- Ce alkylthio, a halo, -CN, or nitro. In certain aspects, R ²³ is methyl, trifluoromethyl, methoxy, methylthio, -CN, nitro, phenyl, or fluoro. In certain aspects, R ²³ is a 5-10 atom heterocyclyl, a C6-C10 aryl, or a 5-10 atom heteroaryl. The remainder of the variables in formulas (I), (II), (la), or (Ila) may be selected as described herein.

|βί35| In certain aspects of the first and second embodiments, no carbon atom of ring A ²³ is substituted. The remainder of the variables in formulas (I), (II), (la), or (Ila) may be selected as described herein.

0Θ36| In certain aspects of the first and second embodiments, at least one carbon atom of ring A ²⁴ is substituted with R ²⁴ . In certain aspects, R ²⁴ is R ⁶ , a C1-C6 alkyl optionally substituted with R ⁶ , a C2-C6 alkenyl optionally substituted with R ⁶ , a C2-C6 alkynyl optionally substituted with R ⁶ , a C3-C10 cycloalkyl optionally substituted with R ⁶ , a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy optionally substituted with R ⁶ , a C1-C6 alkylthio, a halo, -CN, or nitro. In certain aspects, R ²⁴ is a C1-C6 alkyl, a C2-C6 alkenyl, a C2-C6 alkynyl, a C3-C10 cycloalkyl, a 5-10 atom heterocyclyl, a C6-C10 aryl, a 5-10 atom heteroaryl, a C1-C6 alkoxy, a C1-C6 alkylthio, a halo, -CN, or nitro. In certain aspects, R ²⁴ is methyl, trifluoromethyl, methoxy, methylthio, -CN, nitro, phenyl, or fluoro. In certain aspects, R ²⁴ is a 5-10 atom heterocyclyl, a C6-C10 aryl, or a 5-10 atom heteroaryl.

{0837} In certain aspects of the first and second embodiments, no carbon atom of ring A ²⁴ is substituted. The remainder of the variables in formulas (I), (II), (la), or (Ila) may be selected as described herein.

f Θ381 In certain aspects of the first and second embodiments, the repeat unit is represented by the following structural formula:

wherein R ¹ is H or a Ci-6 alkyl; a C6-C10 aryl, or a 5-10 atom heteroaryl; and R ³ is H or a C6-C10 aryloxy. In certain aspects, R ¹ is a Ci-6 alkyl. In certain aspects, R ² is a 5-10 atom heterocyclyl, a C6-C10 aryl, or a 5-10 atom heteroaryl. In certain aspects, R ³ is H.

[0β39| In certain aspects of the first and second embodiments, the polymer is a homopolymer. 101)40} In certain aspects of the first and second embodiments the polymer is a copolymer.

{00 11 In certain aspects of the first and second embodiments, the repeat unit has a structure according to any one of the structural formulas depicted below:

{00421 In a third embodiment, the present disclosure provides methods of catalyzing a hydrogenation reaction, comprising reducing a double or triple carbon-carbon bond with molecular hydrogen in the presence of the polymer-palladium complex of any one of the first or second embodiments or any aspect thereof.

0431 I ^{n a} fourth embodiment, the present disclosure provides methods of catalyzing a Suzuki or Heck coupling reaction, comprising forming a carbon-carbon bond in the presence of the polymer-palladium complex of any one of the first or second embodiments or any aspect therof.

{00441 Synthetic chemists seeking sustainable routes toward target materials often find inspiration in biological systems. Nature delivers countless chemical transformations under ambient conditions, all in an aqueous environment. In this sense, the metalloenzymes responsible for many of these reactions serve as potential models for the design of industrially relevant and sustainable catalytic systems. Despite its role as an excellent Pd ligand and the moiety's omnipresence in natural metalloribozymes, pyrimidine-bearing polymers have yet to be explored in this context.

|0i451 The synthesis of poly(«¾eto-arylene oxides) (poly(«¾AOs), also known as poly(meta- phenylene) oxides, or poly(«¾POs)) enables a convenient route to such pyrimidine-bearing amphiphillic polymers as main-chain polymer ligands, as well as those containing bidentate 1,10-phenanthroline ligands. Unlike many of the more conventional polymers thus far used as metalloenzyme mimics, these poly(«¾AOs) offer facile tuning by the incorporation and variation of side chain groups, while leaving the fundamental backbone unchanged. Just as the suite of amino acids enables nature to regulate the placement and identity of side chain groups in metalloenzymes, so too does this double SNAr modular synthesis allow tuning of groups directly involved in metal binding, or even those at positions farther removed from the 'active site' that can still influence catalytic activity.

|0@46| Reaction of dihalide electrophilic (A) and diphenol nucleophilic (B) coupling partners affords these relatively unexplored, thermooxidatively robust ABAB type poly(«¾AOs).

Typically, the diphenol and electrophile (pyrimidine, pyrazine, pyridine, triazine, or nitro-, nitrile, or acetylene-substituted benzene) coupling partners will react to form small cyclic oligomers (oxacalixarenes). However, with specific electrophiles, poly (m AOs) can be generated under kinetic conditions. Prior studies demonstrated the kinetic polymerization using two electrophilic scaffolds, 4,6-dichloropyrimidines, and 2,6-dihalobenzonitriles. Such

polymerizations are described, for example, in U.S. Patent Pub. No. 2017/0009032. The present disclosure expands the scope of poly(«¾AOs) derived from 4,6-dichloropyrimidines (Al), and introduce 4,7-dichloro- 1, 10-phenanthroline (A2) as a multicyclic aromatic electrophile previously unused in either poly(«¾AO) or oxacalixarene syntheses. In this way, metallo-enzyme inspired, industrially relevant, recyclable catalysts for aqueous Suzuki, Heck, and hydrogenation reactions can be prepared that are effective in the PPM-PPB metal loading range. Scheme 1. Tunable Synthesis of Poly(«¾AOs)

DEFINITIONS

{0i4?l Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of, chemistry described herein, are those well-known and commonly used in the art.

|0i 81 The symbol " " refers to an optional double bond between carbon atoms or between heteroatoms defined below..

[0Θ49| The term "phenylene" refers to a divalent phenyl group.

|βί50| An "alkyl" group is a straight chained or branched non-aromatic hydrocarbon, completely saturated, having the specified number of atoms. Typically, a straight chained or branched alkyl group has from 1 to about 20 carbon atoms, preferably from 1 to about 10 unless otherwise defined. Examples of straight chained and branched alkyl groups include methyl, ethyl, n- propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, pentyl and octyl. 0051 Moreover, the term "alkyl" as used throughout the specification, examples, and claims is intended to include both "unsubstituted alkyls" and "substituted alkyls", the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more substitutable carbons of the hydrocarbon backbone. Such substituents, if not otherwise specified, can include, for example, a halogen (e.g., fluoro), a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), an alkoxy, a phosphoryl, a phosphate, a phosphonate, a phosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyl, an aralkyl, or an aromatic or heteroaromatic moiety. In preferred embodiments, the substituents on substituted alkyls are selected from Ci-6 alkyl, C3-6 cycloalkyl, halogen, carbonyl, cyano, or hydroxyl. In more preferred embodiments, the substituents on substituted alkyls are selected from fluoro, carbonyl, cyano, or hydroxyl. It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain can themselves be substituted, if appropriate. For instance, the substituents of a substituted alkyl may include substituted and unsubstituted forms of amino, azido, imino, amido, phosphoryl (including phosphonate and phosphinate), sulfonyl (including sulfate, sulfonamido, sulfamoyl and sulfonate), and silyl groups, as well as ethers, alkylthios, carbonyls (including ketones, aldehydes, carboxylates, and esters), -CF3, -CN and the like. Exemplary substituted alkyls are described below. Cycloalkyls can be further substituted with alkyls, alkenyls, alkoxys, alkylthios, aminoalkyls, carbonyl-substituted alkyls, -CF3, -CN, and the like.

{0&52| The term "acyl" is art- recognized and refers to a group represented by the general formula hydrocarbyl-C(O)-, for example, alkyl-C(O)-, where "alklyl" is defined above.

Examples of acyls include H ₃ C-C(0)-, H ₃ C-C ₂ H ₂ -C(0)-, etc.

(0053 The term "acylamino" is art-recognized and refers to an amino group substituted with an acyl group and may be represented, for example, by the formula alkyl-C(0)-NH-.

J0054| The term "acyloxy" is art-recognized and refers to a group represented by the general formula hydrocarbyl-C(0)0-, for example alkyl-C(0)0-.

|0055 The term "alkoxy" refers to an alkyl group, having an oxygen attached thereto.

Representative alkoxy groups include methoxy, trifluoromethoxy, ethoxy, propoxy, tert-butoxy and the like. [00561 The term "alkoxyalkyl" refers to an alkyl group substituted with an alkoxy group and may be represented by the general formula alkyl-O-alkyl.

[0057| The term "alkenyl", as used herein, refers to an aliphatic group containing at least one double bond and is intended to include both "unsubstituted alkenyls" and "substituted alkenyls", the latter of which refers to alkenyl moieties having substituents replacing a hydrogen on one or more carbons of the alkenyl group. Typically, a straight chained or branched alkenyl group has from 1 to about 20 carbon atoms, preferably from 1 to about 10 unless otherwise defined. Such substituents may occur on one or more carbons that are included or not included in one or more double bonds. Moreover, such substituents include all those contemplated for alkyl groups, as discussed below, except where stability is prohibitive. For example, substitution of alkenyl groups by one or more alkyl, carbocyclyl, aryl, heterocyclyl, or heteroaryl groups is

contemplated.

58| The term "C _x - _y " when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups that contain from x to y carbons in the chain. For example, the term "C _x - _y alkyl" refers to substituted or unsubstituted saturated hydrocarbon groups, including straight- chain alkyl and branched-chain alkyl groups that contain from x to y carbons in the chain, including haloalkyl groups. Preferred haloalkyl groups include trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl. Co alkyl indicates a hydrogen where the group is in a terminal position, a bond if internal. The terms "C ₂ - _y alkenyl" and "C ₂ -y alkynyl" refer to substituted or unsubstituted unsaturated aliphatic groups analogous in length and possible substitution to the alkyls described above, but that contain at least one double or triple bond respectively.

[005 1 The terms "amine" and "amino" are art-recognized and refer to both unsubstituted and substituted amines and salts thereof, e.g., a moiety that can be represented by f fM Ol wherein each R ^A independently represents a hydrogen or a hydrocarbyl group, or two R ^A are taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure. J0061) The term "alkylamino", as used herein, refers to an amino group substituted with at least one alkyl group.

[0062) The term "alkylthio", as used herein, refers to a thiol group substituted with an alkyl group and may be represented by the general formula alkylS-.

|0063j The term "arylthio", as used herein, refers to a thiol group substituted with an alkyl group and may be represented by the general formula arylS-.

0064) The term "alkynyl", as used herein, refers to an aliphatic group containing at least one triple bond and is intended to include both "unsubstituted alkynyls" and "substituted alkynyls", the latter of which refers to alkynyl moieties having substituents replacing a hydrogen on one or more carbons of the alkynyl group. Typically, a straight chained or branched alkynyl group has from 1 to about 20 carbon atoms, preferably from 1 to about 10 unless otherwise defined. Such substituents may occur on one or more carbons that are included or not included in one or more triple bonds. Moreover, such substituents include all those contemplated for alkyl groups, as discussed above, except where stability is prohibitive. For example, substitution of alkynyl groups by one or more alkyl, carbocyclyl, aryl, heterocyclyl, or heteroaryl groups is

contemplated.

f006SJ The term "amide", as used herein, refers to a group

wherein each R independently represent a hydrogen or hydrocarbyl group, or two R are taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure.

100661 The term "aminoalkyl", as used herein, refers to an alkyl group substituted with an amino group.

f0067| The term "aralkyl", as used herein, refers to an alkyl group substituted with an aryl group. £0068) The term "aryl" as used herein include substituted or unsubstituted aromatic groups having a specified number of atoms in which each atom of the aromatic system is carbon. The ring can be a 6- or 20-membered ring, e.g., a 6-membered ring. The term "aryl" includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is aromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls. Aryl groups include benzene, naphthalene, phenanthrene, phenol, aniline, and the like.

[0069| The term "carbamate" is art-recognized and refers to a group

f 8070J wherein each R independently represent hydrogen or a hydrocarbyl group, such as an alkyl group, or both R ^A taken together with the intervening atom(s) complete a heterocycle having from 4 to 8 atoms in the ring structure.

[ΘΘ711 The terms "carbocycle", and "carbocyclic", as used herein, refers to a saturated or unsaturated ring in which each atom of the ring is carbon. A carbocylic group can have from 3 to 20 carbon atoms. The term carbocycle includes both aromatic carbocycles and non-aromatic carbocycles. Non-aromatic carbocycles include both cycloalkane rings, in which all carbon atoms are saturated, and cycloalkene rings, which contain at least one double bond. "Carbocycle" includes 5-7 membered monocyclic and 8-12 membered bicyclic rings. Each ring of a bicyclic carbocycle may be selected from saturated, unsaturated and aromatic rings. Carbocycle includes bicyclic molecules in which one, two or three or more atoms are shared between the two rings. The term "fused carbocycle" refers to a bicyclic carbocycle in which each of the rings shares two adjacent atoms with the other ring. Each ring of a fused carbocycle may be selected from saturated, unsaturated and aromatic rings. In an exemplary embodiment, an aromatic ring, e.g., phenyl, may be fused to a saturated or unsaturated ring, e.g., cyclohexane, cyclopentane, or cyclohexene. Any combination of saturated, unsaturated and aromatic bicyclic rings, as valence permits, is included in the definition of carbocyclic. Exemplary "carbocycles" include cyclopentane, cyclohexane, bicyclo[2.2.1 ]heptane, 1 ,5-cyclooctadiene, 1,2,3,4- tetrahydronaphthalene, bicyclo[4.2.0]oct-3-ene, naphthalene and adamantane. Exemplary fused carbocycles include decalin, naphthalene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]octane, 4,5,6,7-tetrahydro-lH-indene and bicyclo[4.1.0]hept-3-ene. "Carbocycles" may be susbstituted at any one or more positions capable of bearing a hydrogen atom.

[0072 A "cycloalkyl" group is a cyclic hydrocarbon which is completely saturated.

"Cycloalkyl" includes monocyclic and bicyclic rings. Preferably, a cycloalkyl group has from 3 to 20 carbon atoms. Typically, a monocyclic cycloalkyl group has from 3 to about 10 carbon atoms, more typically 3 to 8 carbon atoms unless otherwise defined. The second ring of a bicyclic cycloalkyl may be selected from saturated, unsaturated and aromatic rings. Cycloalkyl includes bicyclic molecules in which one, two or three or more atoms are shared between the two rings. The term "fused cycloalkyl" refers to a bicyclic cycloalkyl in which each of the rings shares two adjacent atoms with the other ring. The second ring of a fused bicyclic cycloalkyl may be selected from saturated, unsaturated and aromatic rings. A "cycloalkenyl" group is a cyclic hydrocarbon containing one or more double bonds.

10(1731 The term "carbocyclylalkyl", as used herein, refers to an alkyl group substituted with a carbocycle group.

10074} The term "carbonate", as used herein, refers to a group -OC02-R ^A , wherein R ^A represents a hydrocarbyl group.

|007S| The term "carboxy", as used herein, refers to a group represented by the formula -CO2H. |OI76j The term "ester", as used herein, refers to a group -C(0)OR ^A wherein R ^A represents a hydrocarbyl group.

|ΘΘ77] The term "ether", as used herein, refers to a hydrocarbyl group linked through an oxygen to another hydrocarbyl group. Accordingly, an ether substituent of a hydrocarbyl group may be hydrocarbyl-O-. Ethers may be either symmetrical or unsymmetrical. Examples of ethers include, but are not limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethers include "alkoxyalkyl" groups, which may be represented by the general formula alkyl-O-alkyl.

{00781 The terms "halo" and "halogen" as used herein means halogen and includes chloro, fluoro, bromo, and iodo.

{ 0791 The terms "hetaralkyl" and "heteroaralkyl", as used herein, refers to an alkyl group substituted with a hetaryl group.

{00801 The term "heteroalkyl", as used herein, refers to a saturated or unsaturated chain of carbon atoms and at least one heteroatom, wherein no two heteroatoms are adjacent.

{00811 The terms "heteroaryl" and "hetaryl" include substituted or unsubstituted aromatic ring structures having a specified number of atoms, for example, 5- to 20-membered rings, 5- to 6- membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms. The terms "heteroaryl" and "hetaryl" also include poly cyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heteroaromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls. Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine, and the like.

j0@$ j The term "heteroatom" as used herein means an atom of any element other than carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen, and sulfur.

|0I 3} The terms "heterocyclyl", "heterocycle", and "heterocyclic" refer to substituted or unsubstituted non-aromatic ring structures, preferably 3- to 20-membered rings, more preferably 3- to 7-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms. The terms "heterocyclyl" and "heterocyclic" also include polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heterocyclic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls. Heterocyclyl groups include, for example, piperidine, piperazine, pyrrolidine, morpholine, lactones, lactams, and the like.

|ΘΘ84| The term "heterocyclylalkyl", as used herein, refers to an alkyl group substituted with a heterocycle group.

|6I85| The term "hydrocarbyl", as used herein, refers to a group that is bonded through a carbon atom, wherein that carbon atom does not have a =0 or =S substituent. Hydrocarbyls may optionally include heteroatoms. Hydrocarbyl groups include, but are not limited to, alkyl, alkenyl, alkynyl, alkoxyalkyl, aminoalkyl, aralkyl, aryl, aralkyl, carbocyclyl, cycloalkyl, carbocyclylalkyl, heteroaralkyl, heteroaryl groups bonded through a carbon atom, heterocyclyl groups bonded through a carbon atom, heterocyclylakyl, or hydroxyalkyl. Thus, groups like methyl, ethoxyethyl, 2-pyridyl, and trifluoromethyl are hydrocarbyl groups, but substituents such as acetyl (which has a =0 substituent on the linking carbon) and ethoxy (which is linked through oxygen, not carbon) are not.

f 0 | The term "hydroxyalkyl", as used herein, refers to an alkyl group substituted with a hydroxy group.

| ^" 8 87| The term "lower" when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups where there are six or fewer non-hydrogen atoms in the substituent. A "lower alkyl", for example, refers to an alkyl group that contains six or fewer carbon atoms. In certain embodiments, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy substituents defined herein are respectively lower acyl, lower acyloxy, lower alkyl, lower alkenyl, lower alkynyl, or lower alkoxy, whether they appear alone or in combination with other substituents, such as in the recitations hydroxyalkyl and aralkyl (in which case, for example, the atoms within the aryl group are not counted when counting the carbon atoms in the alkyl substituent).

(0088) The terms "polycyclyl", "polycycle", and "polycyclic" refer to two or more rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls) in which two or more atoms are common to two adjoining rings, e.g., the rings are "fused rings". Each of the rings of the polycycle can be substituted or unsubstituted. In certain embodiments, each ring of the polycycle contains from 3 to 10 atoms in the ring, preferably from 5 to 7.

|0Θ89| In the phrase "poly(«¾eto-phenylene oxides)", the term "phenylene" refers inclusively to

6-membered aryl or 6-membered heteroaryl moieties. Exemplary poly(«¾eto-phenylene oxides) are described in the first through twentieth aspects of the present disclosure.

βθ90| The term "silyl" refers to a silicon moiety with three hydrocarbyl moieties attached thereto.

f0§91 J The term "substituted" refers to moieties having substituents replacing a hydrogen on one or more carbons of the backbone. It will be understood that "substitution" or "substituted with" includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. Moieties that may be substituted can include any appropriate substituents described herein, for example, acyl, acylamino, acyloxy, alkoxy, alkoxyalkyl, alkenyl, alkyl, alkylamino, alkylthio, arylthio, alkynyl, amide, amino, aminoalkyl, aralkyl, carbamate, carbocyclyl, cycloalkyl, carbocyclylalkyl, carbonate, ester, ether, heteroaralkyl, heterocyclyl, heterocyclylalkyl, hydrocarbyl, silyl, sulfone, or thioether. As used herein, the term

"substituted" is contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, the heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. Substituents can include any substituents described herein, for example, a halogen, a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), an alkoxy, a phosphoryl, a phosphate, a phosphonate, a phosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamido, a sulfonyl, a heterocyclyl, an aralkyl, or an aromatic or heteroaromatic moiety. In preferred embodiments, the substituents on substituted alkyls are selected from Ci-6 alkyl, C3-6 cycloalkyl, halogen, carbonyl, cyano, or hydroxyl. In more preferred embodiments, the substituents on substituted alkyls are selected from fluoro, carbonyl, cyano, or hydroxyl. It will be understood by those skilled in the art that substituents can themselves be substituted, if appropriate. Unless specifically stated as "unsubstituted," references to chemical moieties herein are understood to include substituted variants. For example, reference to an "aryl" group or moiety implicitly includes both substituted and unsubstituted variants.

|ΘΘ92] The term "sulfonate" is art-recognized and refers to the group SO3H, or a

pharmaceutically acceptable salt thereof.

[0893J The term "sulfone" is art-recognized and refers to the group -S(0) ₂ -R ^A , wherein R ^A represents a hydrocarbyl, for example, an alkyl or an aryl, having a specified number of atoms. |ΘΘ94| The term "sulfinate" is art-recognized and refers to the group SO2H, or a

pharmaceutically acceptable salt thereof.

{0895} The term "sulfine" is art-recognized and refers to the group -S(O) -R ^A , wherein R ^A represents a hydrocarbyl.

(ΘΘ96Ί The term "thioether", as used herein, is equivalent to an ether, wherein the oxygen is replaced with a sulfur.

{ΘΘ97} The term "Suzuki coupling" is art-recognized and refers to the formation of a carbon- carbon bond between a boron-functionalized organic compound (e.g., a boronic acid, potassium trifluoroborate, organoborane, or boronate ester) and a halide or pseudohalide (e.g. a bromide, chloride, fluoride, or triflate (trifluoromethanesulfonate)), with concomitant elimination of the boron group and the halide or pseudohalide. As understood by those of skill in the art, the organic substrates useful in Suzuki couplings include, e.g., aryls, alkyls, alkenyls, and alkynyls. } i9$l The term "Heck coupling" is art-recognized and refers to the formation of a carbon- carbon bond between an aryl halide or vinyl halide (or their pseudohalide equivalents) and an activated alkene in the presence of a base, with concomitant elimination of the halide.

|0099} The term "Sonogashira coupling" is art-recognized and refers to the formation of a carbon-carbon bond between a terminal alkyne and an aryl halide or vinyl halide (or their pseudohalide equivalents), with concomitant elimination of the halide.

EXAMPLES

} 10 j The invention now being generally described, it will be more readily understood by reference to the following examples which are included merely for purposes of illustration of certain aspects and embodiments of the present invention, and are not intended to limit the invention.

Example 1 : General Procedures

10101} The polymers disclosed herein may be prepared via double SNAr between a 1,3-dihalide electrophile and a nucleo hilic 1,3-diphenol (for instance, the reaction depicted in Scheme 2).

Scheme 2

f 81021 The polymerization is tolerant of a variety of functional groups on both the electrophilic and nucleophilic monomers.

1 1 3 Various protogenic groups may be incorporated into these polymers to allow proton transport through them. The SNAT polymerization technique allows precise control over functional group identity and location, as well as the possibility to alternate functional groups down the length of the backbone. Since many other polymerization techniques are incompatible with protogenic moieties such as sulfuric, phosphonic, and carboxylic acids or other hydrogen bonding functionalities, these groups are often added in later steps, yielding incompletely and irregularly functionalized polymers.

10104} Sulfuric, phosphonic, and carboxylic acid groups have varying effects on the proton conductivity of otherwise identical polymer backbones. Loading of protogenic groups may be varied from 50% of residues (i.e., at least one protogenic group on every other residue) to 100% (i.e., at least one protogenic group on each residue).

Example 2: Preparation of ffl-diphenols (10):

{0105} 3,5-dihydroxybenzenesulfonic acid (10a): Under an ambient atmosphere in a 50 rriL round bottom flask charged with a magnetic stir bar were combined benzene-l,3,5-triol (1 gram, 7.9 mmol), NaS ₂ 05 (5.82 grams, 35 mmol), and distilled water (7.75 ml). The reaction was refluxed for 48 hours. The solution was diluted with ethanol, allowed to stand overnight and filtered. The product was recovered in a 94% yield.

{01 61 3,5-dihydroxybenzoic acid (10b): purchased from Acros Organics (97%) and used with no further purification.

[0107| (3,5-dihydroxyphenyl)phosphonic acid (10c): Into a standard 30 mL microwave vial charged with a magnetic stir bar were added: l-bromo-3,5-dimethoxybenzene (12.0 mmol, 2.62 g), triethylphosphite (14.4 mmol, 2.6 mL), NiCk (1.2 mmol, 154 mg). The vial was irradiated in a CEM discover microwave reactor at 160°C for 2 hours. After completion of the reaction, the crude product was purified by silica gel flash column chromatography (eluent: step gradient of 3% to 9% MeOH in CH2CI2) to afford diethyl (3,5-dimethoxyphenyl)phosphonate in a 84% isolated yield. Refluxing in concentrated HBr for 24 hours, followed by neutralization with K2CO3 afforded the (3,5-dihydroxyphenyl)phosphonic acid in a quantitative yield. Removal of water under a reduced pressure provided the (3,5-dihydroxyphenyl)phosphonic acid along with various reaction salts (which were not considered a hindrance to the subsequent polymerization, so were not further separated from the desired product— but they were thoroughly mixed to ensure homogeneity). The percent mass of desired 10c in the lOc/salts mixture was determined by NMR spectroscopy with an internal standard.

[81081 (3,5-dihydroxybenzyl)phosphonic acid (lOd): Into a standard 30 mL microwave vial charged with a magnetic stir bar were added: l-(bromomethyl)-3,5-dimethoxybenzene (17.5 mmol, 4.04 g), and triethyl phosphite (17.5 mmol, 3.0 mL). The vial was irradiated in a CEM discover microwave reactor at 160°C for 2 hours. After completion of the reaction, the crude product was purified by silica gel flash column chromatography (eluent: step gradient of 3% to 9% MeOH in CH2CI2) to afford diethyl (3,5-dimethoxybenzyl)phosphonate in a 93% isolated yield. Refluxing in concentrated HBr for 24 hours, followed by neutralization with K2CO3 afforded the (3,5-dihydroxybenzyl)phosphonic acid (lOd) in a quantitative yield. Removal of water under a reduced pressure provided the (3,5-dihydroxyphenyl)phosphonic acid along with various reaction salts (which were not considered a hindrance to the subsequent polymerization, so were not further separated from the desired product— but they were thoroughly mixed to ensure homogeneity). The percent mass of desired lOd in the lOd/salts mixture was determined by NMR spectroscopy with an internal standard.

[0109| Resorcinol (lOe): purchased from Sigma Aldrich and used with no further purification. Example 3: Source or Preparation of aryl m-dihalides (11):

[01101 2,6-difluorobenzonitrile (11a): purchased from Acros Organics (97%) and used with no further purification.

[01111 3,5-dichloro-4-pyrimidinecarbonitrile (lib): purchased from Sigma Aldrich (97%) and used with no further purification.

[01121 4,6-dichloropyrimidine (11c): purchased from Sigma Aldrich (97%) and used with no further purification.

[0113 4,6-dichloro-2-methylpyrimidine (lid): purchased from TCI (98%) and used with no further purification.

[0114{ Fenchlorim (lie): purchased from Toronto Research Chemicals and used with no further purification.

[011Sj 4,6-dichloropyrimidine-2-carboxylic acid (111): purchased from Sigma Aldrich and used with no further purification.

[0116| 2,3,5,6-tetrafluorobenzotrifluoride (llg): purchased from Oakwood Chemicals and used with no further purification.

[01171 Diethyl (2,6-difluorophenyl)phosphonate (111): Into a standard 30 mL microwave vial charged with a magnetic stir bar were added: 2-bromo-l,3-difluorobenzene (18 mmol, 3.8 g), triethylphosphite (21.6 mmol, 3.9 mL), NiCk (1.6 mmol, 200 mg). The vial was irradiated in a CEM discover microwave reactor at 160°C for 2 hours. After completion of the reaction, the crude product was purified by silica gel flash column chromatography (eluent: step gradient of 3% to 9% MeOH in CH2CI2) to afford diethyl (3,5-dimethoxyphenyl)phosphonate in a 84% isolated yield. Example 4: Synthesis of poly(mAO)s

|βϊ ί8| Poly(«¾AOs) were readily prepared by the reaction of a 1 ,3-diphenol with an equimolar amount of dihalogenated electrophile and excess K2CO3 in DMSO at 100-150°C. General methods for preparing poly(mAO)s, are provided in Wackerly et al, Macromolecules 200, 42, 8181-8186. The preparation of exemplary poly(mAO)s of formula (III) is described below.

|01 J9J Without directly affecting the site of metal-binding, the hydrophobicity of the polymer systems could be tuned by varying the nature of R ¹ (H, methyl, w-pentyl) on the diphenol unit. The coordination environment of the heteroaryl (e.g., pyrimidine) units could likewise be modulated by varying R ² from among H, Ph, N-morpholino, or even by the incorporation of a second pyrimidyl unit, enabling incorporation of a 2,2-bipyrimidine scaffold integrated into the polymer backbone. Alternatively, the bidentate 1,10-phenanthroline unit could be directly incorporated by use of the 4,7-dichloro- 1 ,10-phenanthroline electrophile.

Pory(mAO) la:

|Θ12 | Under an inert atmosphere, resorcinol (13.5 mmol), 4,6-dicholoropyrimidine (13.5 mmol) and anhydrous DMSO (20 mL) were combined. Upon reaching solution homogeneity, anhydrous K2CO3 (20 grams) was added, and the reaction was immediately placed in an aluminum heating block at 100°C and stirred vigorously for 40 minutes. The reaction was quenched by diluting with DMSO (80 mL) and precipitated in 1 L of distilled water. After stirring to break up large particles, the precipitate was filtered, rinsed with water (300 mL), and acetone (100 mL), and dried under vacuum. GC measurement of molecular weight yielded M _n =2337 Da, M _w = 10620 Da, and M _z =15821 Da. Pory(mAO) le:

|β! 21.1 Under an inert atmosphere, orcinol (2.14 mmol, 265 mg), 4-(4,6-Dichloro-2- pyrimidyl)morpholine (2.14 mmol, 0.5 g) and anhydrous DMSO (4 mL) were combined. Upon reaching solution homogeneity, anhydrous K2CO3 (4 grams) was added, and the reaction was immediately placed in an aluminum heating block at 100°C and stirred vigorously for 40 minutes. The reaction was quenched by diluting with DMSO (10 mL) and precipitated in 300 mL of distilled water. After stirring to break up large particles, the precipitate was filtered, rinsed with water (100 mL), and acetone (100 mL), and dried under vacuum.

Pory(mAO) If:

0!22| Under an inert atmosphere, orcinol (2.86 mmol, 355.8 mg), 4,6-Dichloro-5-(2- methoxyphenoxy)-2,2'-bipyrimidine (2.866 mmol, 1.0 gram) and anhydrous DMSO (4.25 mL) were combined. Upon reaching solution homogeneity, anhydrous K2CO3 (4.25 grams) was added, and the reaction was immediately placed in an aluminum heating block at 100°C and stirred vigorously for 40 minutes. The reaction was quenched by diluting with DMSO (80 mL) and precipitated in 1 L of distilled water. After stirring to break up large particles, the precipitate was filtered, rinsed with water (300 mL), and acetone (100 mL), and dried under vacuum. GC measurement of molecular weight yielded M _n =12360 Da, M _w =48615 Da. Polv(mAO) lg:

[0123| Under an inert atmosphere, orcinol (1 mmol, 124 mg), 4,7-dichloro-l,10-phenanthroline (1 mmol) and anhydrous DMSO (2 mL) were combined. Upon reaching solution homogeneity, anhydrous K2CO3 (1.5 grams) was added, and the reaction was immediately placed in an aluminum heating block at 150°C and stirred vigorously for 40 minutes. The reaction was quenched by diluting with DMSO (10 mL) and precipitated in 1 L of distilled water. After stirring to break up large particles, the precipitate was filtered, rinsed with water (100 mL), and acetone (100 mL), and dried under vacuum. GC analysis showed a molecular weight of over

100 kDa.

Pory(mAO) lh

[01241 Under an inert atmosphere, olivetol (2 mmol, 360 mg), 4,7-dichloro-l,10-phenanthroline (2 mmol, 496 mg) and anhydrous DMSO (4 mL) were combined. Upon reaching solution homogeneity, anhydrous K2CO3 (3 grams) was added, and the reaction was immediately placed in an aluminum heating block at 150°C and stirred vigorously for 40 minutes. The reaction was quenched by diluting with DMSO (20 mL) and precipitated in 1 L of distilled water. After stirring to break up large particles, the precipitate was filtered, rinsed with water (100 mL), and acetone (100 mL), and dried under vacuum. GC analysis showed a molecular weight of over

100 kDa.

Example 4: Synthesis of Pd(¾poly(mAO)s Pd@Polv(mAO) la:

I0125J To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) la (1 mmol of repeat unit, 186 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl ₄ (0.15 mmol, 42 mg) in water (2 mL) was added. The solution was left to stir at 60°C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL).

Pd@Polv(mAO) lb:

10126} To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) lb (1 mmol of repeat unit, 200 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl ₄ (0.15 mmol, 42 mg) in water (2 mL) was added. The solution was left to stir at 60°C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL).

Pd@Polv(mAO) lc:

0127| To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) lb (1 mmol of repeat unit, 256 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl ₄ (0.15 mmol, 42 mg) in water (2 mL) was added. The solution was left to stir at 60°C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL).

Pd@Polv(mAO) Id:

[0I 28| To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) Id (1 mmol of repeat unit, 276.1 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl4 (0.15 mmol, 42 mg) in water (2 mL) was added. The solution was left to stir at 60°C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL). Pd@Polv(mAO) le:

(0129} To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) le (0.3 mmol of repeat unit, 85.5 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl ₄ (0.045 mmol, 12.78 mg) in water (2 mL) was added. The solution was left to stir at 60°C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL).

Pd@Polv(mAO) If:

{01301 To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) If (1 mmol of repeat unit, 384.13 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl ₄ (0.15 mmol, 42.6 mg) in water (2 mL) was added. The solution was left to stir at 60° C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL).

Pd@Polv(mAO) lg:

6 31} To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) lg (1 mmol of repeat unit, 281.3 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl4 (0.15 mmol, 42.6 mg) in water (2 mL) was added. The solution was left to stir at 60° C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL).

Pd@Polv(mAO) lh:

[0132J To a 10 mL round bottom, screw-top vial with a stir bar was added Poly(mAO) lh (1 mmol of repeat unit, 372 mg) and CHCh (2 mL). The mixture was stirred at 60°C until reaching solution homogeneity, at which point a solution of (NH ₄ )2PdCl ₄ (0.15 mmol, 42 mg) in water (2 mL) was added. The solution was left to stir at 60°C for another 3 hours, then cooled to room temperature, diluted with acetone (4 mL), washed with H2O (20 mL), acetone (20 mL), and chloroform (20 mL). Example 5: Coordinative Convolution of Poly(mAOs):

fill33j Coordinative convolution of each polymer was achieved by mixing a solution of (NH ₄ )2PdCl4 (0.15 mmol in 2 mL H ₂ 0) into a solution of poly(«¾AO) (1 mmol in 2 mL CHCh). After stirring vigorously for 3 hours at 60°C, the mixture was diluted with acetone, and the globular, insoluble Pd-polymer complex was washed with H2O, acetone, and chloroform. XPS analysis of the resultant (NH ₄ )2PdCl ₄ @poly(«¾AOs) indicated Pd present as mostly PdCb with some PdO (FIG. 1 A). TEM analysis identified PdO nanoparticles (3.2 +/- 0.6 nm) distributed evenly throughout the polymer matrix (FIG. IB). SEM/EDX elemental mapping likewise demonstrated an even distribution of both Pd and CI (FIG. 1C and FIG. ID). Loading of each Pd@Poly(«¾AO) complex was carried out via ICP-MAS, ranging from 0.32-0.89 mmol/gram. The coordination of Pd to multiple pyrimidine or phenanthroline ligands serves the dual role of cross-linking the polymer and stabilizing the reactive metal center.

Example 6: Aqueous Hydrogenation:

10134} Styrene hydrogenation catalyzed by (NH ₄ )2PdCl ₄ @Poly(«¾AO)la-c was evaluated in order to probe the relative effect of pendant side chain groups not directly involved in metal binding, (FIG. 2). By increasing the hydrophobicity (R ¹ = H < CH3 < C5H11), the yield for styrene hydrogenation decreased in cyclohexane (94 - 42%), but steadily increased in water (52% - 95%). The increased reactivity in water likely stems from the more hydrophobic polymer's ability to better attract the nonpolar styrene into the polymer matrix to interact with the active palladium species.

fO Sj Aqueous hydrogenations catalyzed by (NH ₄ )2PdCl ₄ @Poly(«¾AO) (lb) were conducted on a variety of additional substrates to evaluate reaction scope. As shown in Table 3, hydrogenation was successful in the reduction of alkyne functional groups to the corresponding alkenes (semi- reduction) and/or the fully reduced alkanes (entries 1, 2, 5, 6). Aldehydes were also reduced to the corresponding benzyl alcohol, with only minor amounts of reduction of the resulting primary alcohol to a methyl group (entries 3,4). Ketone reduction was much more sluggish, forming the secondary alcohol in only 10% yield under the same conditions for aldehyde reduction (entry 7). Table 3. Additional Hydrogenation Reactions catalyzed by (NH4)2PdCl4(¾Poly(fflAO)lb

15 mg Pd@poly(mPO) 1b

Starting Material (0.5 mmol) Product

H ₂ (balloon)

water, 25 °C, 24 h

Entr Startin Material Product (Yield)

(10%)

Example 7: Aqueous Suzuki Coupling:

f#I36| Suzuki coupling under aerobic and aqueous conditions was explored. These conditions tend to be problematic for Pd/phosphine systems. For this reaction, the full range of as-prepared Pd@Poly(«¾AOs) was explored, and no advantage was found to hydrophobicity tuning nor the more complicated bidentate phenanthroline or bipyrimidyl systems (SI), so proceeded with the simplest polymer (Poly(«¾AO)la) was used for further testing. Given the expense and sensitivity of aryl bromides and iodides, the study sought conditions which could effectively catalyze the coupling of aryl boronic acids with electron deficient (Table 3, entry 3) and even electron rich (Entries 4-6) aryl chlorides. In order to allow reactivity with especially sluggish boronic acids, aryl iodides and bromides were not strictly ignored. Indeed, coupling to the far less reactive iram-2-phenylvinyl boronic acid proceeded smoothly with bromo- and iodobenzene (Entry 7). Likewise, in order to demonstrate a high TON (Entry 9), coupling of 4-iodotoluene with phenylboronic acid was carried out at a Pd loading of 400 mol PPM (99 %), 40 mol PPM (97%), 4 mol PPM (99%), and 400 mol PPB (75%, TON = 1.9 million). In order to demonstrate the reusability of the catalyst, the initial reaction rates for recycling runs were compared (Entry 8). Through 5 cycles of catalysis, the initial reaction rate did not significantly decrease. In further support of a heterogeneous mechanism, it was found that (NH4)2PdCl4 was incapable of catalyzing the coupling of aryl chlorides to phenylboronic acid even with the addition of the closest available homogeneous analogue (4,6-dimethoxypyrimidine) to the polymeric complex, indicating the cooperative affect of the Pd/polymer complex. Furthermore, ICP analysis after catalysis likewise demonstrated very little (0.17 PPB) Pd leached from the polymer matrix during the course of the reaction.

Table 3. Aqueous Suzuki Coupling

Pd@Poly(mPO) „ „

Ar-X + R-B(OH) ₂ ► Ar-R

TBAB (optional), K ₃ P0 ₄ ,

H ₂ 0, 95°C

Entry Ar R Yield ³ (X: %)

1 4-Me-C ₆ H ₄ Ph CI: 97 (isolated)

2 Ph 4-Me-C ₆ H ₄ CI: 98 (GC)

3 4-CN-CeH4 Ph CI: 97 (isolated)

4 4-NH ₂ -C ₆ H ₄ Ph CI: 94 (isolated)

5 4-OH-CeH4 Ph CI: 95 (isolated)

6 4-OMe-C ₆ H ₄ Ph CI: 94 (isolated)

7 Ph I: 98, (Isolated) Br: 95, (GC) CI:

1 (GC)

8 4-Me-C ₆ H ₄ Ph CI (initial rates, μιηοΐ/ιηίη):

1.4, ^c 1.3, ^d 1.5, ^e 1.4/ 1.3 ^g

9 4-Me-C ₆ H ₄ Ph I: 99, ^h 97/ 99,J 75 ^k (GC)

10 4-Me-C ₆ H ₄ Ph CI: trace (homogeneous) ^{1 a} reaction conditions: (NH ₄ )2PdCl4@Poly(«¾AO)lb (10 mg, 0.04 mol%), Ar- X (1.5 mmol), R-B(OH) ₂ (1.8 mmol), TBAB ( ^a 1.5 mmol, 0 mmol), K3PO4

(4.5 mmol), H2O (0.6 mmol), 95°C, 20 hr.

Initial rates of recycling reactions ^c : (NH4)2PdCl4@Poly(«¾AO)lb (10 mg, 0.04 mol%), Ar-X (1.5 mmol), R-B(OH) ₂ (1.8 mmol), TBAB (1.5 mmol), K3PO4

(4.5 mmol), H ₂ Q (0.6 mmol), 95°C, 3 hr. ( ^d 2 ^nd , ^e 3 ^rd , ^f 4 ^th , ^g 5 ^fe ) Demonstration of High TON: (NH ₄ ) ₂ PdCl ₄ @Poly(fl¾AO)lb ( ^h 10 mg, 40 PPM, 1 1 mg, 4 PPM, ^J 0.1 mg, 0.4 PPM, ^k 0.1 mg, 400 PPB), Ar-X ( ^{h iJ} 1.5 mmol, ^k 15 mmol), R-B(OH) ₂ ( ^{h iJ} 1.8 mmol, ^k 18 mmol), K ₃ P0 ₄ ( ^{h iJ} 4.5 mmol, ^k 45 mmol), H ₂ 0 ( ^{h iJ} 0.6 mL ^k 6 mL), 95 °C, 20 hr.

Homogeneous Reactivity Test: (NH ₄ )2PdCl ₄ (1.2 mg), 4,6- dimethoxypyrimidine (4.7 mg), Ar-X (1.5 mmol), R-B(OH>2 (1.8 mmol),

TBAB (1.5 mmol), K ₃ PQ ₄ (4.5 mmol), H2O (0.6 mmol), 95°C, 20 hr.

Example 8: Aqueous Heck Coupling

[Θ137| In order to further showcase the versatility of this catalyst platform, its utility in mediating Heck coupling under aqueous conditions was investigated (Table 4).

Table 4. Aqueous Heck Coupling

(NH ₄ )PdCI ₄ @Poly(mPO)1a (0.1 mol%)

^Ar"x K3PO4 (2.0 mmol), H ₂ 0 (2.0 mL), ^Ar

1.0 mmol 2.0 mmol 95'C, 20 hr

Entry Ar R Yield ³ (X: %)

Ϊ Ph CO2BU I: 95 (GC), Br: 62 (GC)

2 Ph Ph I: 67 (GC)

{0138} Heck coupling reactions under aqueous using (NH ₄ )2PdCl ₄ @Poly(«¾AO)lb were also investigated on more complex substrates (Table 5).

Table 5. Additional Aqueous Heck Reactions catalyzed by ( H4)2PdC14(¾Polv(mAO)lb

20 mg Pd@poly(mPO) 1b

Ar-X ₊ Vinyl-Ar *· Product

(2 mmol) (4 mmol) water (4 mL), 100 °C, 48 h

K ₃ P0 ₄ (4 mmol)

E

Example 9. Sonogashira Coupling:

{01391 Sonogashira coupling was carried out with (NH ₄ )2PdCl ₄ @Poly(«¾AO) (lb) between aryl iodides (iodobenzene or 4-iodotoluene) and terminal alkynes (phenyl acetylene or l-ethynyl-4- methylbenzene), each for the production of the same product: 1 -methyl-4- (phenylethynyl)benzene. These reactions were carried out at 100°C for 20 hours either in water (with the addition of K2CO3) or in Et3N (with no additional base). The reaction proceeded with slightly higher yields under aqueous conditions (61% & 55%) as compared to the triethylamine base/solvent system (48 & 53%).

Table 6. Sonogashira Coupling catalyzed by (NH4)2PdC14@Poly(mAOHb

Ar-I + > 10 mg Pd @ poly(m PO) 1 b

(1 mmol) R'

100°C, 20 hour, solvent (3 mL),

(1.2 mmol) _K2C o ₃ (optional: 2 mmol)

Entry Ar-I Product

R

(Yield)

a Conditions: 100°C, 20 h, water (3 ml), K ₂ C0 ₃

" Conditions: 100°C, 20 h, Et ₃ N (3 mL)

References

All publications and patents mentioned herein are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control.

Equivalents

While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this specification and the claims below. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations.