Charge-bearing cyclodextrin polymeric materials and methods of making and using same

1. A porous polymeric material comprising a plurality of cyclodextrins crosslinked with a plurality of aryl diisocyanate crosslinkers, wherein one or more of the plurality of cyclodextrins are bound to a linker of formula (I):

wherein

A is an aryl moiety;

each R 1 is independently H or C 1 -C 6 alkyl;

each R 2 is independently H or alkyl;

each W is independently a bond, an alkylene group, an arylene group, a heteroarylene group, —O-arylene-, —(CH 2 ) a -arylene-, —SO 2 -arylene-, —NH-arylene-, —S-arylene-, —O— heteroarylene-, —(CH 2 ) a -heteroarylene-, —SO 2 -heteroarylene-, —NH-heteroarylene-, —S-heteroarylene-, —(—O—(CH 2 ) a —) x —, —(—NH—(CH 2 ) a —) x —, —(—S—(CH 2 ) a —) x —,

 wherein a is 0-100 and x is 1-100, and each arylene or heteroarylene moiety can be substituted or unsubstituted;

each Z is a cationic moiety;

each L is

A′ is a covalent bond to A;

Z′ is a covalent bond to Z;

* is a covalent bond to ;

is a point of attachment to the plurality of cyclodextrin carbon atoms;

x is 0-8;

y 1 is 1-4;

y 2 is 1-4; and

y 3 is 0-4.

2. The porous polymeric material of claim 1 , wherein each Z is independently —N(R 3 ) 3 + , —P(R 3 ) 3 + , —S(R 3 ) 2 + , or heteroaryl + , wherein each R 3 is independently —H, —C 1 -C 6 alkyl, —C 1 -C 3 haloalkyl, -aryl, —C(O)N(R a )(R b ), —C(O)R c , ═CO 2 R c , —SO 2 N(R a )(R b ), or —SOR c , wherein each R a , R b and R c is independently H or C 1 -C 6 alkyl.

3. The porous polymeric material of claim 2 , wherein Z is —N(R 3 ) 3 + .

4. The porous polymeric material of claim 2 , wherein W is

5. The porous polymeric material of claim 4 , wherein Z is —N(R 3 ) 3 + .

6. The porous polymeric material of claim 1 , wherein each instance of —W—Z is taken together to form

7. The porous polymeric material of claim 1 , wherein each cyclodextrin is independently selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

8. The porous polymeric material of claim 1 , wherein R 1 and R 2 are H.

9. The porous polymeric material of claim 1 , wherein the aryl moiety is

wherein represents any of the substituents attached to A in formula (I).

10. The porous polymeric material of claim 9 , wherein the plurality of aryl diisocyanate crosslinkers comprise 4,4′-methylene diphenyl diisocyanate, 2,4′-methylene diphenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or combinations thereof;

the aryl moiety is selected from the group consisting of

and combinations thereof;

each R 1 is H; and

each R 2 is H or alkyl.

11. The porous polymeric material of claim 10 , wherein the plurality of aryl diisocyanate crosslinkers comprise 4,4′-methylene diphenyl diisocyanate.

12. The porous polymeric material of claim 10 , wherein each Z is independently —N(R 3 ) 3 + , —P(R 3 ) 3 + , —S(R 3 ) 2 + , or heteroaryl + , wherein each R 3 is independently —H, —C 1 -C 6 alkyl, —C 1 -C 3 haloalkyl, -aryl, —C(O)N(R a )(R b ), —C(O)R c , ═CO 2 R c , —SO 2 N(R a )(R b ), or —SOR c , wherein each R a , R b , and R c is independently H or C 1 -C 6 alkyl.

13. The porous polymeric material of claim 12 , wherein Z is —N(R 3 ) 3 + .

14. The porous polymeric material of claim 12 , wherein W is

15. The porous polymeric material of claim 14 , wherein Z is —N(R 3 ) 3 + .

16. The porous polymeric material of claim 10 , wherein each instance of —W—Z is taken together to form

17. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 10 , whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.

18. A method of purifying a fluid sample comprising one or more pollutants, the method comprising contacting the fluid sample with the porous polymeric material of claim 1 , whereby at least 50 wt. % of the total amount of the one or more pollutants in the fluid sample is adsorbed by the porous polymeric material.