Macrocyclic module compositions

Abstract

Macrocyclic module compositions are made from cyclic synthons. The macrocyclic module structures are prepared by stepwise or concerted schemes which couple synthons in a closed ring. The macrocyclic module structures may have a pore of nanometer dimensions.

The claimed invention is:  
     
         1 . A macrocyclic module composition comprising: 
 from three to about twenty-four cyclic synthons coupled to form a closed ring;    at least two functional groups for coupling the closed ring to complementary functional groups on at least two other closed rings;    wherein each functional group and each complementary functional group comprises 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.    
     
     
         2 . The composition of  claim 1 , comprising at least two closed rings coupled through said functional groups.  
     
     
         3 . The composition of  claim 1 , comprising at least three closed rings coupled through said functional groups.  
     
     
         4 . A macrocyclic module composition comprising: 
 from three to about twenty-four cyclic synthons coupled to form a closed ring defining a pore;    the closed ring having a first pore dimension in a first conformation when a first group of substituents is located at the pore and a second pore dimension in a second conformation when a second group of substituents is located at the pore;    wherein each substituent of each group comprises 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.    
     
     
         5 . A composition, comprising: 
 (a) from three to about twenty-four cyclic synthons coupled to form a closed ring defining a pore;    (b) at least one functional group coupled to the closed ring at the pore and selected to transport a selected species through the pore, wherein the at least one functional group comprises 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;    (c) a selected species to be transported through the pore.    
     
     
         6 . The composition of  claim 5 , wherein the selected species is selected from the group of ovalbumin, glucose, creatinine, H 2 PO 4   − , HPO 4   −2 , HCO 3   − , urea, Na + , Li + , and K + .  
     
     
         7 . 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.  
   
     
     
         8 . The composition as in any one of claims  1 - 4  coupled to a solid support selected from the group of Wang resins, hydrogels, aluminas, metals, ceramics, polymers, silica gels, sepharose, sephadex, agarose, inorganic solids, semiconductors, and silicon wafers.  
     
     
         9 . The composition as in any one of claims  1 - 4 , wherein the macrocyclic module composition retains at least 85% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         10 . The composition as in any one of claims  1 - 4 , wherein the macrocyclic module composition retains at least 95% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         11 . The composition as in any one of claims  1 - 4 , wherein the macrocyclic module composition retains at least 98% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         12 . The composition as in any one of claims  1 - 5 , wherein the cyclic synthons are each independently selected from the group consisting of benzene, cyclohexadiene, cyclohexene, cyclohexane, cyclopentadiene, cyclopentene, cyclopentane, cycloheptane, cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctane, cyclooctene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, naphthalene, anthracene, phenylene, phenanthracene, pyrene, triphenylene, phenanthrene, pyridine, pyrimidine, pyridazine, biphenyl, bipyridyl, decalin, piperidine, pyrrolidine, morpholine, piperazine, pyrazolidine, quinuclidine, tetrahydropyran, dioxane, tetrahydrothiophene, tetrahydrofuran, pyrrole, triptycene, adamantane, bicyclo[2.2.1]heptane, bicyclo[2.2.1]heptene, bicyclo[2.2.2]octane, bicyclo[2.2.2]octene, bicyclo[3.3.0]octane, bicyclo[3.3.0]octene, bicyclo[3.3.1]nonane, bicyclo[3.3.1]nonene, bicyclo[3.2.2]nonane, bicyclo[3.2.2]nonene, bicyclo[4.2.2]decane, 7-azabicyclo[2.2.1]heptane, 1,3-diazabicyclo[2.2.1]heptane, and spiro[4.4]nonane.  
     
     
         13 . The composition as in any one of claims  1 ,  4 , or  5 , wherein each coupled cyclic synthon is independently coupled to two adjacent synthons by a linkage 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 —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
       
         
           
           
               
               
           
         
         wherein p is 1-6;  
         wherein R and R′ are each independently selected from the group of hydrogen and alkyl;  
         wherein the linkage is 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 Q is one of the synthons connected by the linkage.  
       
     
     
         14 . A closed ring composition of the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 J is 2-23;  
 Q 1  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 Q 1  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;  
 Q 2  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 Q 2  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 —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
                     
  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 Q y  are each independently one of the Q 1  or Q 2  synthons connected by the linkage.  
 
     
     
         15 . The composition of  claim 14 , wherein the organic functional groups are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 , —C(O)CH═CH(C 6 H 5 ),  
       
         
           
           
               
               
           
         
       
       —OH, —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 , —P(O)(OH)(OX), —P(═O)(O − )O(CH 2 ) s NR 3   + ; 
 wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4.  
 
     
     
         16 . The composition of  claim 14 , wherein the macrocyclic module composition retains at least 85% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         17 . The composition of  claim 14 , wherein the macrocyclic module composition retains at least 95% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         18 . The composition of  claim 14 , wherein the macrocyclic module composition retains at least 98% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         19 . A closed ring composition of the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 J is 2-23;  
 Q 1  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 Q 1  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;  
 Q 2  is a cyclohexane synthon coupled to linkages L at 1,2-cyclohexyl positions; wherein ring positions of Q 2  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 —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
                     
  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 Q y  are each independently one of the Q 1  or Q 2  synthons connected by the linkage.  
 
 
     
     
         20 . The composition of  claim 19 , wherein the organic functional groups are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 , —C(O)CH═CH(C 6 H 5 ),  
       
         
           
           
               
               
           
         
       
       —OH, —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 , —P(O)(OH)(OX), —P(═O)(O − )O(CH 2 ),NR 3   + ; 
 wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4.  
 
     
     
         21 . The composition of  claim 19 , wherein the macrocyclic module composition retains at least 85% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         22 . The composition of  claim 19 , wherein the macrocyclic module composition retains at least 95% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         23 . The composition of  claim 19 , wherein the macrocyclic module composition retains at least 98% of film area after thirty minutes on a Langmuir trough at 5-15 mN/m.  
     
     
         24 . A closed ring composition of the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 J is 2-23;  
 Q 1  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 Q 1  is a phenyl synthon coupled to linkages L at 1,4-phenyl positions, and wherein ring positions of each Q 1  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;  
 Q 2  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 Q 2  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 —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
                     
  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 Q y  are each independently one of the Q 1  or Q 2  synthons connected by the linkage.  
 
     
     
         25 . The composition of  claim 24 , wherein the organic functional groups are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 , —C(O)CH═CH(C 6 H 5 ),  
       
         
           
           
               
               
           
         
       
       —OH, —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 , —P(O)(OH)(OX), —P(═O)(O − )O(CH 2 ) s NR 3   + ; 
 wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4.  
 
     
     
         26 . A closed ring composition of the formula:  
       
         
           
           
               
               
           
         
       
       wherein: 
 Q is  
                     
  J is from 1-22, and n is from 1-24;  
 X and R n  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 —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CHCH 2 CH═N— —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —P(O)(OH) 2 O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
                     
  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.  
 
     
     
         27 . The composition of  claim 26 , wherein X and R n  are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl,  
       
         
           
           
               
               
           
         
       
       —C(O)CH═CH 2 , —NHC(O)CH═CH 2 , —C(O)CH═CH(C 6 H 5 ),  
       
         
           
           
               
               
           
         
       
       —OH, —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 , and, —P(O)(OH)(OX), —P(═O)(O − )O(CH 2 ) s NR 3   + ; 
 wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4.  
 
     
     
         28 . A closed ring composition of the formula:  
       
         
           
           
               
               
           
         
       
       wherein:  
       
         
           
           
               
               
           
         
         J is from 1-22, and n is from 1-48;  
         X and R n  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 —, —CH 2 NH—, —C(O)S—, —C(O)—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
         
           
             
             
                 
                 
             
           
         
          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.  
       
     
     
         29 . The composition of  claim 28 , wherein X and R n  are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl,  
       
         
           
           
               
               
           
         
       
       —C(O)CH═CH 2 , —NHC(O)CH═CH 2 , —C(O)CH═CH(C 6 H 5 ),  
       
         
           
           
               
               
           
         
       
       —OH, —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 , and, —P(O)(OH)(OX), —P(═O)(O − )O(CH 2 ) s NR 3   + ; 
 wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4.  
 
     
     
         30 . The composition of  claim 14  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein:  
       
         
           
           
               
               
           
         
         J is from 1-11, and n is from 1-12;  
         X and R n  are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 ,  
          —C(O)CH═CH(C 6 H 5 ),  
         
           
             
             
                 
                 
             
           
         
         —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 ,  
                           
—P(O)(OH)(OX), —P(═O)(O 31  )O(CH 2 ) s NR 3   + ;  
         wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4;  
         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 —NRC(O)—, —OC(O)—, —O—, —S—S—, —S—, —NR—, —(CRR′) p —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
         
           
             
             
                 
                 
             
           
         
          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.  
       
     
     
         31 . The composition of  claim 19  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein:  
       
         
           
           
               
               
           
         
         J is from 1-11, and n is from 1-12;  
         X and R n  are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 ,  
          —C(O)CH═CH(C 6 H 5 ),  
         
           
             
             
                 
                 
             
           
         
         —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 ,  
                           
—P(O)(OH)(OX), —P(═O)(O 31  )O(CH 2 ) s NR 3   + ;  
         wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4;  
         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 —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
         
           
             
             
                 
                 
             
           
         
          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.  
       
     
     
         32 . The composition of  claim 14  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein:  
       
         
           
           
               
               
           
         
          J is from 1-11, and n is from 1-12;  
         X is —NX 1 — or —CX 2 X 3 , where 
 X 1  is selected from the group consisting of an amino acid residue, —CH 2 C(O)CH 2 CH(NH2)CO 2 -alkyl, and —C(O)CH═CH 2 ;  
 X 2  and X 3  are each independently selected from the group consisting of hydrogen, —OH, —NH 2 , —SH, —(CH 2 ) t OH, —(CH 2 ) t NH 2  and —(CH 2 ) t SH, wherein t is 1-4, and X 2  and X 3  are not both hydrogen;  
 
         R n  are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 , —C(O)CH═CH(C 6 H 5 ),  
         
           
             
             
                 
                 
             
           
         
          —OH, —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 , —P(O)(OH)(OX), —P(═O)(O 31  )O(CH 2 ) s NR 3   + ;  
         wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4;  
         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 —NRC(O)—, —OC(O)—, —O—, —S—S—, —S—, —NR—, —(CRR′) p —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
         
           
             
             
                 
                 
             
           
         
          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.  
       
     
     
         33 . The composition of  claim 14  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein:  
       
         
           
           
               
               
           
         
         J is from 1-11, and n is from 1-12;  
         X and R n  are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 , —C(O(CH═CH(C 6 H 5 ),  
         
           
             
             
                 
                 
             
           
         
          —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 ,  
                           
—P(O)(OH)(OX), —P(═O)(O 31  )O(CH 2 ) s NR 3   + ;  
         wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4;  
         Z and Y 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 —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
         
           
             
             
                 
                 
             
           
         
          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.  
       
     
     
         34 . The composition of  claim 14  having the formula:  
       
         
           
           
               
               
           
         
       
       wherein:  
       
         
           
           
               
               
           
         
         J is from 1-11, and n is from 1-12;  
         X and R n  are each independently selected from the group consisting of hydrogen, an activated acid, —OH, —C(O)OH, —C(O)H, —C(O)OCH 3 , —C(O)Cl, —NRR, —NRRR + , —MgX, —Li, —OLi, —OK, —ONa, —SH, —C(O)(CH 2 ) 2 C(O)OCH 3 , —NH-alkyl-C(O)CH 2 CH(NH 2 )CO 2 -alkyl, —CH═CH 2 , —CH═CHR, —CH═CR 2 , 4-vinylaryl, —C(O)CH═CH 2 , —NHC(O)CH═CH 2 ,  
         
           
             
             
                 
                 
             
           
         
          —C(O)CH═CH(C 6 H 5 ), —OC(O)(CH 2 ) 2 C(O)OCH 3 , —OC(O)CH═CH 2 , —P(O)(OH)(OX), —P(═O)(O 31  )O(CH 2 ) s NR 3   + ;  
         wherein R are each independently selected from the group consisting of hydrogen and 1-6C alkyl; X is selected from the group consisting of Cl, Br, and I; r is 1-50; and s is 1-4;  
         Z and Y 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 —NRC(O)—, —OC(O)—, —O—, —S—S—, —S—, —NR—, —(CRR′) p —, —CH 2 NH—, —C(O)S—, —C(O)O—, —C≡C—, —C≡C—C≡C—, —CH(OH)—, —HC═CH—, —NHC(O)NH—, —NHC(O)O—, —NHCH 2 NH—, —NHCH 2 CH(OH)CH 2 NH—, —N═CH(CH 2 ) p CH═N—, —CH 2 CH(OH)CH 2 —, —N═CH(CH 2 ) h CH═N— where h is 1-4, —CH═N—NH—, —OC(O)O—, —OP(O)(OH)O—, —CH(OH)CH 2 NH—, —CH(OH)CH 2 —, —CH(OH)C(CH 3 ) 2 C(O)O—,  
         
           
             
             
                 
                 
             
           
         
          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.  
       
     
     
         35 . A method for making a macrocyclic module composition comprising: 
 (a) providing a plurality of a first cyclic synthon;    (b) contacting a plurality of a second cyclic synthon with the first cyclic synthons;    (c) isolating the macrocyclic module composition.    
     
     
         36 . The method of  claim 35 , further comprising contacting a linker molecule with the mixture in (a) or (b).  
     
     
         37 . A method for making a macrocyclic module composition comprising: 
 (a) providing a plurality of a first cyclic synthon;    (b) contacting a plurality of a second cyclic synthon with the first cyclic synthons;    (c) contacting a plurality of the first cyclic synthon with the mixture from (b).    
     
     
         38 . A method for making a macrocyclic module composition comprising: 
 (a) providing a plurality of a first cyclic synthon;    (b) contacting a plurality of a second cyclic synthon with the first cyclic synthons;    (c) contacting a plurality of a third cyclic synthon with the mixture from (b).    
     
     
         39 . The method of  claim 37  or  38 , further comprising supporting a cyclic synthon or coupled synthons on a solid phase.  
     
     
         40 . A method for making a macrocyclic module composition comprising: 
 (a) contacting a plurality of cyclic synthons with a metal complex template;    (b) isolating the macrocyclic module composition.