Supramolecular assemblies and building blocks
The present invention generally relates to supramolecular assemblies and their modes of synthesis. The supramolecular assemblies include a 1:8 ratio of a supermolecular polyhedral building block and a triangular molecular building block, the supermolecular polyhedral building block having points of extension corresponding to the vertices of a rhombicuboctahedron for linking the supermolecular polyhedral building block to the triangular building block.
1. A supramolecular assembly comprising a 1:8 ratio of a supermolecular polyhedral building block and a triangular molecular building block, the supermolecular polyhedral building block having points of extension corresponding to the vertices of a rhombicuboctahedron for linking the supermolecular polyhedral building block to the triangular building blocks wherein an individual supermolecular polyhedral building block is linked to twenty-four different triangular building blocks and an individual triangular building block is linked to three different supermolecular polyhedral building blocks, the linkages comprising covalent bonds, coordinate covalent bonds, noncovalent bonds, or a combination thereof.
2. The supramolecular assembly of claim 1 wherein the supramolecular assembly is a metal-organic framework.
3. The supramolecular assembly of claim 2 wherein the metal-organic supermolecular polyhedral building block and the triangular molecular building block comprise copper.
4. The supramolecular assembly of claim 2 wherein the supramolecular building block and the triangular building block are derived from the assembly of a metal and a ligand corresponding to Formula (2):
wherein
the X ring comprises a monocyclic ring or polycyclic fused ring system, or has the formula:
each A ring is a monocyclic ring or polycyclic fused ring system;
each L 1 and L 3 is a linker moiety;
each L 5 is a linker moiety;
each R 1 and R 3 is a functional group capable of coordinately bonding to at least one metal;
each D ring is a monocyclic ring or a polycyclic fused ring system;
M 1 , M 2 , and M 3 are independently metal ions; and
the dashed lines represent coordination between the nitrogen atom of a D ring and a metal.
5. The supramolecular assembly of claim 4 wherein the A rings are a benzene, boroxine, or triazine ring.
6. The supramolecular assembly of claim 4 wherein the X ring is a benzene ring.
7. The supramolecular assembly of claim 4 wherein L 1 is a bond or -(L 11 ) m -, wherein L 11 is hydrocarbylene or substituted hydrocarbylene and m is a positive integer, and L 3 is a bond or -(L 33 ) m -, wherein L 33 is hydrocarbylene or substituted hydrocarbylene and n is a positive integer, with L 1 and L 3 being the same.
8. The supramolecular assembly of claim 4 wherein the metal is a transition metal.
9. The supramolecular assembly of claim 4 wherein L 1 and L 3 is a bond.
10. The supramolecular assembly of claim 4 wherein the metal is L 1 and L 3 are the same and are substituted or unsubstituted phenylene.
11. The supramolecular assembly of claim 4 wherein L 5 is a bond or -(L 555 ) m -, wherein L 555 has the formula: —NH—, —C(═O)—NH—, —C(═O)—O—, —R y —O—, —O—C(═O)—NH—, —SO 2 —NH—, or —NH—C(═O)—NH—, wherein R y is alkylene, and m is a positive integer.
12. The supramolecular assembly of claim 4 wherein R 1 and R 3 are bidentate functional groups.
13. The supramolecular assembly of claim 4 wherein R 1 and R 3 are carboxylic acid (—CO 2 H) groups.
14. The supramolecular assembly of claim 1 wherein the supramolecular building block and the triangular building block are derived from the assembly of a metal and a ligand having the formula:
wherein
the A ring is a monocyclic ring or polycyclic fused ring system;
each L 1 and L 3 is a linker moiety;
L 5 is a linker moiety;
each R 1 and R 3 is a functional group capable of coordinately bonding to at least one metal;
the D ring is a monocyclic ring or a polycyclic fused ring system; and
the -L 1 -R 1 , -L 3 -R 3 , and -L 5 -D ring moieties are positioned about 120° from each other.
15. The supramolecular assembly of claim 14 wherein the A ring is a benzene, boroxine, or triazine ring.
16. The supramolecular assembly of claim 14 wherein the A ring is a benzene ring.
17. The supramolecular assembly of claim 14 wherein the ligand has the formula:
wherein the D ring and the D 1 , D 2 , and D 5 ring atoms define a pyrazolyl, triazolyl, or tetrazolyl ring, provided that at least one of D 1 , D 2 , and D 5 is a carbon atom.
18. The supramolecular assembly of claim 14 wherein the ligand corresponds to Formula (1B):
19. The supramolecular assembly of claim 18 wherein L 1 is a bond or -(L 11 ) m -, wherein L 11 is hydrocarbylene or substituted hydrocarbylene and m is a positive integer, and L 3 is a bond or -(L 33 ) m -, wherein L 33 is hydrocarbylene or substituted hydrocarbylene and n is a positive integer, with L 1 and L 3 being the same.
20. The supramolecular assembly of claim 18 wherein L 1 and L 3 are each a bond or -(L 111 ) m - and -(L 333 ) m -, respectively, wherein L 111 and L 333 have the formula: —NH—, —C(═O)—NH—, —C(═O)—O—, —R y —O—, —O—C(═O)—NH—, —SO 2 —NH—, or —NH—C(═O)—NH—, wherein R y is alkylene, and m is a positive integer.
21. The supramolecular assembly of claim 18 wherein L 1 and L 3 is a bond.
22. The supramolecular assembly of claim 18 wherein L 1 and L 3 are the same and are substituted or unsubstituted alkylene, or substituted or unsubstituted arylene.
23. The supramolecular assembly of claim 18 wherein L 1 and L 3 are the same and are substituted or unsubstituted phenylene.
24. The supramolecular assembly of claim 18 wherein L 5 is a bond or -(L 55 ) m -, wherein L 55 is hydrocarbylene or substituted hydrocarbylene and m is a positive integer.
25. The supramolecular assembly of claim 18 wherein L 5 is a bond or -(L 555 ) m -, wherein L 555 has the formula: —NH—, —C(═O)—NH—, —C(═O)—O—, —R y —O—, —O—C(═O)—NH—, —SO 2 —NH—, or —NH—C(═O)—NH—, wherein R y is alkylene, and m is a positive integer.
26. The supramolecular assembly of claim 18 wherein L 5 is a bond.
27. The supramolecular assembly of claim 18 wherein L 5 is substituted or unsubstituted phenylene.
28. The supramolecular assembly of claim 18 wherein R 1 and R 3 are bidentate functional groups.
29. The supramolecular assembly of claim 18 wherein R 1 and R 3 are carboxylic acid (—CO 2 H) groups.
30. The supramolecular assembly of claim 18 wherein the metal is a transition metal.
31. A process for the preparation of a supramolecular assembly, the process comprising combining a metal source and a ligand to generate a composition comprising a 1:8 ratio of a supermolecular polyhedral building block and a triangular molecular building block, the supermolecular polyhedral building block having points of extension corresponding to the vertices of a rhombicuboctahedron for linking the supermolecular polyhedral building block to the triangular building blocks wherein an individual supermolecular polyhedral building block is linked to twenty-four different triangular building blocks and an individual triangular building block is linked to three different supermolecular polyhedral building blocks, the linkages comprising covalent bonds, coordinate covalent bonds, noncovalent bonds, or a combination thereof.