Diversity-oriented polymers of intrinsic microporosity and uses thereof

A method for preparing a microporous polymer, the method comprising

• forming a polymerization mixture comprising
• (1) a plurality of A-A monomers, wherein each A-A monomer is independently a compound according to Formula (I), (II), (III), (IV), (V), (VI), (VII), or (VIII)
• or Formula (Ia), (IIa), (IIa), (IVa), (Va), (VIa), (VIIa), or (VIIIa):
• (2) a plurality of B-B monomers, wherein each B-B monomer is independently a compound according to Formula (i), (ii), (iii), (iv), (v), (vi), (vii), or (viii):
• wherein X is a halide, and
• (3) a base, and
• heating the polymerization mixture, thereby forming the microporous polymer, wherein the microporous polymer is of the formula:
• -[A-AB-B]n—,
• or a salt thereof;
• wherein:
• n is an integer ranging from 10 to 10,000;
• each monomer segment A-A is independently a monomer segment according to Formula (A), (B), (C), (D), (E), (F), (G) or (H):
• each monomer segment B-B is independently a monomer segment according to Formula (a), (b), (c), (d), (e), or (f):
• each R11 is independently selected from the group consisting of —CH2NR1R2 and H;
• each R12 is independently selected from the group consisting of —C(NOR13)N(R14)2 and —CN;
• at least one R11 in at least one monomer segment A-A is —CH2NR1R2, or at least one R12 in at least one monomer segment B-B is —C(NOR13)N(R14)2;
• each R1 and R2 is independently selected from the group consisting of (C1-29)alkyl, (C2-20)alkenyl, (C2-20)alkynyl, (C6-12)aryl, (C3-8)cycloalkyl, (C6-12)alkyl(C1-20)alkyl, (C3-8)cycloalkyl(C1-20)alkyl, hetero(C1-20)alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C1-20)alkyl, 5- to 8-membered heteroaryl, heteroaryl(C1-20)alkyl,
• wherein each R1 and R2 is optionally and independently substituted with one or more Z1,
• wherein ach alkyl, alkenyl, and alkynyl in R1 and R2 optionally and independently comprises one or more heteroatoms independently selected from silicon, a chalcogenide, and a pnictide, and
• wherein one or more atoms in R1 and R2 are optionally and independently present in oxidized form as C═O, C═S, N═O, N═S, S═O or S(O)2;
• or
• alternatively, each R1 is optionally and independently taken together with R2, and the nitrogen atom to which both are attached, to form 3-, to 8-membered heterocyclyl or 5- to 8-member heteroaryl, each of which is optionally substituted with one or more Z2;
• each Z1 and Z2 is independently selected from the group consisting of halogen, —OH, —NO2, —CN, (C1-20)alkyl, (C2-20)alkenyl, (C2-20)alkynyl, (C6-12)aryl, (C3-8)cycloalkyl, (C6-12)aryl(C1-20)alkyl, hetero(C1-20)alkyl, 3- to 8-membered heterocyclyl, 5- to 8-membered heteroaryl, (C1-8)cycloalkyl-(C1-20)alkyl, 3- to 8-membered heterocyclyl-(C1-20)alkyl, 5- to 8-membered heteroaryl-(C1-20)alkyl, halo(C1-20)alkyl, halo(C1-20)alkyloxy, —OR6, —SR6, —S(O)R6, —S(O)2R6, —SO2NR6R7, —NR6C(O)R7, —NR6S(O)2R7, —NR6C(O)NR7R8, —NR6R7, —CO2R6, —C(O)NR6R7, and —C(O)R6;
• each R3, R4, R5, R6, R7, and R8 is independently selected from the group consisting of (C1-20)alkyl, (C2-20)alkenyl, (C2-20)alkynyl, (C6-12)aryl, (C3-8)cycloalkyl, (C6-12)aryl(C1-20)alkyl, (C3-8)cycloalkyl(C1-20)alkyl, hetero(C1-20)alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C1-20)alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C1-20)alkyl, 5- to 8-membered heteroaryl, 5- to 8-membered heteroaryl-(C1-20)alkyl;
• or
• alternatively, R4 and R5 are taken together to from (C4-8)cycloalkyl, (C6-12)aryl, 4- to 8-membered heterocyclyl, or 5- to 8-membered heteroaryl;
• or
• alternately, R6 and R7 are taken together to form 4- to 8-member heterocycl or 5- to 8-membered heteroaryl;
• or
• alternately, R7 and R8 are taken together to form 4- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl;
• each R13 is selected from the group consisting of H, (C1-20)alkyl, and (C3-8) cycloalkyl, wherein alkyl and cycloalkyl are optionally and independently substituted with one or more Z3;
• provided and R13 is (C1-20)alkyl or (C3-8)cycloalkyl, each of which is optionally and independently substituted with one or more Z3, when all R11 groups in monomer segments according to formula (A) are H;
• each R14 is independently selected from the group consisting of H, (C1-20)alkyl, and (C3-8)cycloalkyl;
• and
• each Z3 is independently selected from the group consisting of halogen, —NO2, —CN, —OH, —SO3H, —NH2, (C1-20)alkyl, (C2-20)alkenyl, (C2-20)alkynyl, (C6-12)alkyl, (C3-8)cycloalkyl, (C6-12)aryl(C1-20)alkyl, hetero(C1-20)alkyl, 3- to 8-membered heterocyclyl, 5- to 8-membered heteroaryl, (C3-8)cycloalkyl-(C1-20)alkyl, 3- to 8-membered heterocycl-(C1-20)alkyl, 5- to 8-membered heteroaryl-(C1-20)alkyl, halo(C1-20)alkyl, halo(C1-20)alkyloxy, —OR6, —SR6, —S(O)R6, —S(O)2R6, —SO2NR6R7, —NR6C(O)R7, —NR6S(O)2R7, —NR6C(O)NR7R8, —NR6R7, —CO2R6, —C(CO)NR6R7, and —C(O)R6.

A compound according to Formula (I), (II), (III), (IV), (V), (VI), (VII), or (VIII):

• or a salt thereof,
• wherein:
• each R1 and R2 is independently selected from the group consisting of (C1-20)alkyl, (C2-20)alkenyl, (C2-20)alkynyl, (C6-12)aryl, (C3-8)cycloalkyl, (C6-12)aryl-(C1-20)alkyl, (C3-8)cycloalkyl(C1-20)alkyl, hetero(C1-20)alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C1-20)alkyl, 5- to 8-membered heteroaryl, 5- to 8-membered heteroaryl-(C1-20)alkyl,
• wherein each R1 and R2 is optionally and independently substituted with one or more Z1,
• wherein each alkyl, alkenyl, and alkynyl in R1 and R2 optionally and independently comprises one or more heteroatoms independently selected from silicon, a chalcogenide, and a pnictide, and
• wherein one or more atoms in R1 and R2 are optionally and independently present in oxidized form as C═O, C═S, N═O, N═S, S═O or S(O)2;
• or
• alternatively, each R1 is optionally and independently taken together with R2, and the nitrogen atom to which both are attached, to form 3- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl, each of which is optionally substituted with one or more Z2;
• each Z1 and Z2 is independently selected from the group consisting of halogen, —OH, —NO2, —CN, (C1-20)alkyl, (C2-20)alkenyl, (C2-20)alkynyl, (C6-12)aryl, (C3-8)cycloalkyl, (C6-12)aryl(C1-20alkyl, hetero(C1-20)alkyl, 3- to 8-membered heterocyclyl, 5- to 8-membered heteroaryl, (C3-8)cycloalkyl(C1-20)alkyl, 3- to 8-membered heterocyclyl-(C1-20)alkyl, 5- to 8-membered heteroaryl-(C1-20)alkyl, halo(C1-20)alkyl, halo(C1-20)alkyloxy, —OR6, —SR6, —S(O)R6, —S(O)2R6, —SO2NR6R7, —NR(C(O)R7, —NR(S(O)2R7, —NRC(O)NR6R8, —NR6R7, —CO2R6, —C(O)NR6R7, and —C(O)R6;
• each R3, R4, R5, R6, R7, and R8 is independently selected from the group consisting of (C1-20)alkyl, (C2-20)alkenyl, (C2-20)alkynyl, (C6-12)aryl, (C3-8)cycloalkyl, (C6-12)aryl(C1-20)alkyl, (C3-8)cycloalkyl(C1-20)alkyl, hetero(C1-20)alkyl, 3- to 8-membered heterocyclyl, 3- to 8-membered heterocyclyl-(C1-20)alkyl, 5- to 8-membered heteroaryl, 5- to 8-membered heteroaryl-(C1-20)alkyl;
• or
• alternatively, R4 and R5 are taken together to form (C4-8)cycloalkyl, (C6-12)aryl, 4- to 8-membered heterocyclyl, or 5- to 8-membered heteroaryl;
• or
• alternatively, R6 and R7 are taken together to form 4- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl;
• or
• alternatively, R7 and R8 are taken together to form 4- to 8-membered heterocyclyl or 5- to 8-membered heteroaryl.