Aryl triazole cages

1. An aryl-triazole bicyclic macrocycle of Formula (I):

wherein R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen.

2. The aryl-triazole bicyclic macrocycle of claim 1 , wherein R 1 , R 2 , and R 3 comprise N,N-dicyclohexylamide groups.

3. The aryl-triazole bicyclic macrocycle of claim 1 , wherein the aryl-triazole bicyclic macrocycle having Formula (I) is selected from the following:

4. A method of synthesizing an aryl-triazole bicyclic macrocycle of Formula (II):

wherein R is independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

the method comprises:

forming a reaction mixture comprising:

wherein

is selected from the group consisting of

or a combination thereof,

wherein R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen;

tripropargylamine; and

a solvent;

incubating the reaction mixture at a reaction temperature above room temperature for a reaction time to form the aryl-triazole bicyclic macrocycle of Formula (II); and

optionally purifying the aryl-triazole bicyclic macrocycle of Formula (II) from the reaction mixture to provide the aryl-triazole bicyclic macrocycle of Formula (II).

5. The method of claim 4 , wherein R is selected from the group consisting of the following:

6. The method of claim 4 , wherein the solvent comprises a Cu(I) source, a reducing reagent and a buffer.

7. The method of claim 6 , wherein the Cu(I) source comprises CuSO 4 .

8. The method of claim 6 , wherein the reducing reagent comprises sodium ascorbate.

9. The method of claim 6 , wherein the buffer comprises tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), tetrahydrofuran (THF), tert-butyl alcohol (t-BuOH), and water (H 2 O).

10. The method of claim 4 , wherein the solvent comprises CuSO 4 , sodium ascorbate and tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), tetrahydrofuran (THF), tert-butyl alcohol (t-BuOH), and water (H 2 O).

11. The method of claim 4 , wherein the reaction temperature comprises a temperature in the range from about 50° C. to about 70° C.

12. The method of claim 4 , wherein the reaction temperature comprises a temperature of about 60° C.

13. The method of claim 4 , wherein the reaction time comprises a reaction time up to and including 5 days.

14. The method of claim 4 , wherein the reaction time comprises a reaction time in a range from about 1 day to about 5 days.

15. The method of claim 4 , wherein the reaction time comprises about 3 days.

16. The method of claim 4 , wherein the step of purifying the aryl-triazole bicyclic macrocycle of Formula (I) comprises chromatography.

17. A method of synthesizing the aryl-triazole bicyclic macrocycle of Formula (I) according to claim 1 ,

the method comprising a first sequence of step-wise reactions, a second sequence of step-wise reactions, a third sequence of step wise reactions, or a fourth sequence of step-wise reactions,

wherein the first sequence of step-wise reactions comprises Reaction 1, Reaction 2, Reaction 3, and Reaction 4,

wherein the second sequence of step-wise reactions comprises Reaction 5, Reaction 3, and Reaction 4,

wherein the third sequence of step-wise reactions comprises Reaction 1, Reaction 2, and Reaction 6,

wherein the fourth sequence of step-wise reactions comprises Reaction 5 and Reaction 6,

wherein Reaction 1 comprises contacting two equivalents of dipropargyl amine with one equivalent of diazido-benzene 1

 (diazido-benzene 1),

to form intermediate 1

 (intermediate 1),

wherein the Reaction 2 comprises contacting intermediate 1 with diazido-benzene 2

 (diazido-benzene 2)

to form MC1-1

 (MC1-1),

wherein Reaction 3 comprises contacting one equivalent of MC1-1 with two equivalents of propargyl bromide to form MC2-1

 (MC2-1);

wherein Reaction 4 comprises contacting MC2-1 with diazido-benzene 3

 (diazido-benzene 3);

to form the aryl-triazole bicyclic macrocycle of Formulas (I);

wherein Reaction 5 comprises contacting one equivalent of diazido-benzene 1 with one equivalent of diazido-benzene 2 and two equivalents of dipropargyl amine to form MC1-1; and

wherein Reaction 6 comprises contacting MC1-1 with triad-1

 (triad 1)

to form the aryl-triazole bicyclic macrocycle of Formulas (I).

18. The method of claim 17 , wherein the aryl-triazole bicyclic macrocycle is Formula (I), wherein at least one of R 1 , R 2 and R 3 differs from the other two R-substituents.

19. The method of claim 17 , wherein the aryl-triazole bicyclic macrocycle is Formula (I), wherein R 1 , R 2 and R 3 differ from each other.

20. The method of claim 17 , wherein the method comprises the first sequence of step-wise reactions.

21. The method of claim 17 , wherein the method comprises a method of step-wise synthesis of the aryl-triazole bicyclic macrocycle of Formula (I) from macrocycle intermediate MC1-1 by an alkylation using Reaction 6.

22. The method of claim 17 , wherein intermediate macrocycle MC1-1 is prepared in a one-pot synthesis using Reaction 5.

23. An aryl-triazole bicyclic macrocycle of Formula (III):

wherein X is independently selected from the group consisting of CH, CF and N,

wherein R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen.

24. The aryl-triazole bicyclic macrocycle of claim 23 , wherein the aryl-triazole bicyclic macrocycle is selected from the group consisting of the following:

25. An aryl-triazole bicyclic macrocycle selected from the group consisting of Formula (IV), (V), (VI) and (VII):

wherein for (IV), n=1 to 10, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O)—N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (V), X and Y are independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 8 , —N(R 9 R 10 ), —CO 2 R 11 , —C(O)—N(R 2 R 3 ), wherein R 8 , R 9 , R 10 R 11 , R 12 , and R 13 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VI), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VII), n=1 to 4, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen.

26. A method of synthesizing an aryl-triazole bicyclic macrocycle selected from Formulas (III), (IV), (V) and (VI):

wherein for (III), X is independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (IV), n=1 to 10, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (V), X and Y are independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 8 , —N(R 9 R 10 ), —CO 2 R 11 , —C(O)—N(R 12 R 13 ), wherein R 1 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VI), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen, the method comprises preparing macrocycle intermediate MC2-1

 (MC2-1) and

contacting MC2-1 with a diazido compound selected from

27. A method of synthesizing an aryl-triazole bicyclic macrocycle of Formula (VII):

wherein n=1 to 4, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O)—N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

the method comprises:

preparing macrocycle intermediate MC1-1:

 (MC1-1); and

alkylating macrocycle intermediate MC1-1 to produce the aryl-triazole bicyclic macrocycle of Formula (VII).

28. A complex comprising:

(a) an anion,

(b) a cation and

(c) an aryl-triazole bicyclic macrocycle selected from the group consisting of Formulas (I), (III), (IV), (V), (VI) and (VII):

wherein for (I), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (III), X is independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (IV), n=1 to 10, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (V), X and Y are independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 8 , —N(R 9 R 10 ), —CO 2 R 11 , —C(O)—N(R 12 R 13 ), wherein R 1 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VI), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VII), n=1 to 4, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen.

29. The complex of claim 28 , wherein the aryl-triazole bicyclic macrocycle is Formula (I) in which R 1 , R 2 , and R 3 comprise N,N-dicyclohexylamide groups.

30. The complex of claim 28 , wherein the aryl-triazole bicyclic macrocycle is selected from the group consisting of the following species of Formula (I):

31. The complex of claim 28 , wherein the anion is selected from Cl − , Br − , I − , CN − , F − , HF 2 − , SCN − , N 3 − , O 2 2− , O 2 2− , NO 2 − , NO 3 − , CO 3 2− , HCO 3 − , S 2− , S n x− , where n=≥1, and x=1 or 2, and ArO − .

32. A method of removing an anion from aqueous solution containing the anion, comprising:

(a) contacting the aqueous solution with an immiscible organic solution comprising an aryl-triazole bicyclic macrocycle selected from the group consisting of Formulas (I), (III), (IV), (V), (VI) and (VII):

wherein for (I), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (III), X is independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (IV), n=1 to 10, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (V), X and Y are independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 8 , —N(R 9 R 10 ), —CO 2 R 11 , —C(O)—N(R 12 R 13 ), wherein R 1 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VI), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R′, —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VII), n=1 to 4, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen;

(b) forming a complex, said complex comprising the anion, a cation and the aryl-triazole bicyclic macrocycle in the organic layer; and

(c) separating the organic layer from aqueous layer.

33. The method of claim 32 , wherein the aryl-triazole bicyclic macrocycle is Formula (I) in which R 1 , R 2 , and R 3 comprise N,N-dicyclohexylamide groups.

34. The method of claim 32 , wherein the aryl-triazole bicyclic macrocycle is selected from the group consisting of the following species of Formula (I):

35. A method of preventing corrosion of a metal surface, comprising:

(a) depositing a solution comprising an aryl-triazole bicyclic macrocycle in a solvent phase onto the metal surface to produce a coating on the metal surface, wherein the aryl-triazole bicyclic macrocycle is selected from the group consisting of Formulas (I), (III), (IV), (V), (VI) and (VII):

wherein for (I), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (III), X is independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (IV), n=1 to 10, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (V), X and Y are independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 8 , —N(R 9 R 10 ), —CO 2 R 11 , —C(O)—N(R 12 R 13 ), wherein R 1 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VI), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VII), n=1 to 4, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen;

(b) removing the solvent phase from the coating to produce a metal surface having dried coating; and

(c) annealing the dried coating onto the metal surface by applying a neat solvent to the metal surface having the dried coating of step (b).

36. The method of claim 35 , wherein the aryl-triazole bicyclic macrocycle is Formula (I) in which R 1 , R 2 , and R 3 comprise N,N-dicyclohexylamide groups.

37. The method of claim 35 , wherein the aryl-triazole bicyclic macrocycle is selected from the group consisting of the following species of Formula (I):

38. A composition comprising a metal surface and a coating, wherein the coating comprises an aryl-triazole bicyclic macrocycle selected from the group consisting of Formulas (I), (III), (IV), (V), (VI) and (VII):

wherein for (I), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (III), X is independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (IV), n=1 to 10, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (V), X and Y are independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 8 , —N(R 9 R 10 ), —CO 2 R 11 , —C(O)—N(R 12 R 13 ), wherein R 1 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VI), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VII), n=1 to 4, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen.

39. The composition of claim 38 , wherein the aryl-triazole bicyclic macrocycle is Formula (I) in which R 1 , R 2 , and R 3 comprise N,N-dicyclohexylamide groups.

40. The complex of claim 38 , wherein the aryl-triazole bicyclic macrocycle is selected from the group consisting of the following species of Formula (I):

41. The composition of claim 38 , wherein the metal surface comprises a metal composed of stainless steel.

42. A formulation, comprising:

a coating; and

an aryl-triazole bicyclic macrocycle selected from the group consisting of Formulas (I), (III), (IV), (V), (VI) and (VII):

wherein for (I), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (III), X is independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (IV), n=1 to 10, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (V), X and Y are independently selected from the group consisting of CH, CF and N, and R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 8 , —N(R 9 R 10 ), —CO 2 R 11 , —C(O)—N(R 12 R 13 ), wherein R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VI), R 1 , R 2 , and R 3 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 4 , —N(R 5 R 6 ), —CO 2 R 7 , —C(O)—N(R 8 R 9 ), wherein R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen,

wherein for (VII), n=1 to 4, and R 1 and R 2 are independently selected from the group consisting of alkenyl, alkyl, alkoxy, alkyl-NH-alkyl, aryl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, hydrogen, iodo, —OR 3 , —N(R 4 R 5 ), —CO 2 R 6 , —C(O) N(R 7 R 8 ), wherein R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of alkenyl, alkyl, aryl, arylalkyl, cycloalkyl, heteroaryl, heterocycle, haloalkyl, and hydrogen.

43. The formulation of claim 42 , wherein the aryl-triazole bicyclic macrocycle is Formula (I) in which R 1 , R 2 , and R 3 comprise N,N-dicyclohexylamide groups.

44. The formulation of claim 42 , wherein the aryl-triazole bicyclic macrocycle is selected from the group consisting of the following species of Formula (I):

45. The formulation of claim 42 , wherein the coating comprises a polymer.

46. The formulation of claim 45 , wherein the polymer is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, acrylic polymers, latex, epoxy and polyester.

47. The formulation of claim 42 , wherein the coating comprises a pigment.

48. The formulation of claim 47 , wherein the pigment comprises a colorant.