Macrocyclic module compositions

A method of preparing a composition to transport a selected species through the composition, comprising:

• selecting a first cyclic synthon, wherein the first cyclic synthon is substituted with at least one functional group comprising an organic functional group containing atoms selected from the group consisting of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• selecting from two to about twenty-three additional cyclic synthons;
• incorporating the first cyclic synthon and the additional cyclic synthons into a macrocyclic module composition comprising:
• from three to about twenty-four cyclic synthons coupled to form a closed ring defining a pore;
• wherein the at least one functional group of the first cyclic synthon is located at the pore of the macrocyclic module composition and is selected to transport the selected species through the pore.

A closed ring composition of the formula:

• 94
• wherein:
• J is 2-23;
• Q1 are synthons each independently selected from the group consisting of (a) phenyl synthons coupled to linkages L at 1,2-phenyl positions, (b) phenyl synthons coupled to linkages L at 1,3-phenyl positions, (c) aryl synthons other than phenyl synthons, (d) heteroaryl synthons other than pyridinium synthons, (e) saturated cyclic hydrocarbon synthons, (f) unsaturated cyclic hydrocarbon synthons, (g) saturated bicyclic hydrocarbon synthons, (h) unsaturated bicyclic hydrocarbon synthons, (i) saturated multicyclic hydrocarbon synthons, and (j) unsaturated multicyclic hydrocarbon synthons;
• wherein ring positions of each Q1 which are not coupled to a linkage L are substituted with hydrogen or organic functional groups containing atoms selected from the group of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• Q2 is a synthon independently selected from the group consisting of (a) aryl synthons other than phenyl synthons and naphthalene synthons coupled to linkages L at 2,7-naphthyl positions, (b) heteroaryl synthons other than pyridine synthons coupled to linkages L at 2,6-pyridino positions, (c) saturated cyclic hydrocarbon synthons other than cyclohexane synthons coupled to linkages L at 1,2-cyclohexyl positions, (d) unsaturated cyclic hydrocarbon synthons other than pyrrole synthons coupled to linkages L at 2,5-pyrrole positions, (e) saturated bicyclic hydrocarbon synthons, (f) unsaturated bicyclic hydrocarbon synthons, (g) saturated multicyclic hydrocarbon synthons, and (h) unsaturated multicyclic hydrocarbon synthons;
• wherein ring positions of Q2 which are not coupled to an L are substituted with hydrogen or organic functional groups containing atoms selected from the group consisting of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• L are linkages between the synthons each independently selected from the group consisting of (a) a condensed linkage, and (b) a linkage selected from the group consisting of —NRC(O)—, —OC(O)—, —O—, —S—S—, —S—, —NR—, —(CRR′)p—, —CH2NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH2NH—, —NHCH2CH(OH)CH2NH—, —N═CH(CH2)pCH═N—, —CH2CH(OH)CH2—, —N═CH(CH2)hCH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH2NH—, —CH(OH)CH2—, —CH(OH)C(CH3)2C(O)O—,
• 95
• wherein p is 1-6;
• wherein R and R′ are each independently selected from the group of hydrogen and alkyl;
• wherein linkages L are each independently configured in either of two possible configurations, forward and reverse, with respect to the synthons it couples together, if the two configurations are different structures;
• wherein y is 1 or 2, and Qy are each independently one of the Q1 or Q2 synthons connected by the linkage.

A closed ring composition of the formula:

• 97
• wherein:
• J is 2-23;
• Q1 are synthons each independently selected from the group consisting of (a) phenyl synthons coupled to linkages L at 1,2-phenyl positions, (b) phenyl synthons coupled to linkages L at 1,3-phenyl positions, and (c) cyclohexane synthons coupled to linkages L at 1,2-cyclohexyl positions;
• wherein ring positions of each Q1 which are not coupled to a linkage L are substituted with hydrogen or organic functional groups containing atoms selected from the group of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• Q2 is a cyclohexane synthon coupled to linkages L at 1,2-cyclohexyl positions;
• wherein ring positions of Q2 which are not coupled to an L are substituted with organic functional groups containing atoms selected from the group consisting of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• L are linkages between the synthons each independently selected from the group consisting of (a) a condensed linkage, and (b) a linkage selected from the group consisting of —NRC(O)—, —OC(O)—, —O—, —S—S—, —S—, —NR—, —(CRR′)p—, —CH2NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH2NH—, —NHCH2CH(OH)CH2NH—, —N═CH(CH2)pCH═N—, —CH2CH(OH)CH2—, —N═CH(CH2)hCH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH2NH—, —CH(OH)CH2—, —CH(OH)C(CH3)2C(O)O—,
• 98
• wherein p is 1-6;
• wherein R and R′ are each independently selected from the group of hydrogen and alkyl;
• wherein linkages L are each independently configured in either of two possible configurations, forward and reverse, with respect to the synthons it couples together, if the two configurations are different structures;
• wherein y is 1 or 2, and Qy are each independently one of the Q1 or Q2 synthons connected by the linkage.

A closed ring composition of the formula:

• 100
• wherein:
• J is 2-23;
• Q1 are synthons each independently selected from the group consisting of (a) phenyl synthons coupled to linkages L at 1,4-phenyl positions, (b) aryl synthons other than phenyl synthons, (c) heteroaryl synthons, (d) saturated cyclic hydrocarbon synthons, (e) unsaturated cyclic hydrocarbon synthons, (f) saturated bicyclic hydrocarbon synthons, (g) unsaturated bicyclic hydrocarbon synthons, (h) saturated multicyclic hydrocarbon synthons, and (i) unsaturated multicyclic hydrocarbon synthons;
• wherein at least one of Q1 is a phenyl synthon coupled to linkages L at 1,4-phenyl positions, and wherein ring positions of each Q1 which are not coupled to a linkage L are substituted with organic functional groups containing atoms selected from the group of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• Q2 is a synthon independently selected from the group consisting of (a) aryl synthons other than phenyl synthons and naphthalene synthons coupled to linkages L at 2,7-naphthyl positions, (b) heteroaryl synthons, (c) saturated cyclic hydrocarbon synthons other than cyclohexane synthons coupled to linkages L at 1,2-cyclohexyl positions, (d) unsaturated cyclic hydrocarbon synthons, (e) saturated bicyclic hydrocarbon synthons, (f) unsaturated bicyclic hydrocarbon synthons, (g) saturated multicyclic hydrocarbon synthons, and (h) unsaturated multicyclic hydrocarbon synthons;
• wherein ring positions of Q2 which are not coupled to an L are substituted with hydrogen or organic functional groups containing atoms selected from the group consisting of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• L are linkages between the synthons each independently selected from the group consisting of (a) a condensed linkage, and (b) a linkage selected from the group consisting of —NRC(O)—, —OC(O)—, —O—, —S—S—, —S—, —NR—, —(CRR′)p—, —CH2NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH2NH—, —NHCH2CH(OH)CH2NH—, —N═CH(CH2)pCH═N—, —CH2CH(OH)CH2—, —N═CH(CH2)hCH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH2NH—, —CH(OH)CH2—, —CH(OH)C(CH3)2C(O)O—,
• 101
• wherein p is 1-6;
• wherein R and R′ are each independently selected from the group of hydrogen and alkyl;
• wherein linkages L are each independently configured in either of two possible configurations, forward and reverse, with respect to the synthons it couples together, if the two configurations are different structures;
• wherein y is 1 or 2, and Qy are each independently one of the Q1 or Q2 synthons connected by the linkage.

A closed ring composition of the formula:

• 103
• wherein:
• Q is
• 104
• J is from 1-22, and n is from 1-24;
• X and Rn are each independently selected from the group consisting of organic functional groups containing atoms selected from the group consisting of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• Z are each independently hydrogen or a lipophilic group;
• L are linkages between synthons each independently selected from the group consisting of (a) a condensed linkage, and (b) a linkage selected from the group consisting of —N═CR—, —NRC(O)—, —OC(O)—, —O—, —S—S—, —S—, —NR—, —(CRR′)p—, —CH2NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH2NH—, —NHCH2CH(OH)CH2NH—, —N═CHCH2CH═N— —N═CH(CH2)hCH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —P(O)(OH)2O—, —CH(OH)CH2NH—, —CH(OH)CH2—, —CH(OH)C(CH3)2C(O)O—,
• 105
• wherein p is 1-6;
• wherein R and R′ are each independently selected from the group of hydrogen and alkyl;
• wherein linkages L are each independently configured in either of two possible configurations, forward and reverse, with respect to the synthons it couples together, if the two configurations are different structures.

A closed ring composition of the formula:

• 108
• wherein:
• 109
• J is from 1-22, and n is from 1-48;
• X and Rn are each independently selected from the group consisting of organic functional groups containing atoms selected from the group consisting of C, H, N, O, Si, P, S, B, Al, halogens, and metals from the alkali and alkaline earth groups;
• Z are each independently hydrogen or a lipophilic group;
• L are linkages between the synthons each independently selected from the group consisting of (a) a condensed linkage, and (b) a linkage selected from the group consisting of —NRC(O)—, —OC(O)—, —O—, —S—S——S—, —NR—, —(CRR′)p—, —CH2NH—, —C(O)S—, —C(O)—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH2NH—, —NHCH2CH(OH)CH2NH—, —N═CH(CH2)pCH═N—, —CH2CH(OH)CH2—, —N═CH(CH2)hCH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH2NH—, —CH(OH)CH2—, —CH(OH)C(CH3)2C(O)O—,
• 110
• wherein p is 1-6;
• wherein R and R′ are each independently selected from the group of hydrogen and alkyl;
• wherein linkages L are each independently configured in either of two possible configurations, forward and reverse, with respect to the synthons it couples together, if the two configurations are different structures.