Redox active triangular organic materials

Patent metadata

Field	Value
Publication number	US-9546169-B2
Application number	US-201514845205-A
Country	US
Kind code	B2
Filing date	Sep 3, 2015
Priority date	Sep 3, 2014
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

Abstract

A redox-active triangular prism is provided. The redox-active triangular prism includes a plurality of pure enantiomers selected from a group consisting of (−)-NDI-Δ and (+)-NDI-Δ. Methods for their preparation as solvent-templated supramolecular structures and a characterization of their redox-active behavior are provided.

First claim

The invention claimed is:

1. A redox-active triangular prism, comprising:
a plurality of pure enantiomers selected from a group consisting of the following:

2. The redox-active triangular prism of claim 1 , wherein the plurality of pure enantiomers form a structure having a central cavity.

3. The redox-active triangular prism of claim 1 , wherein the central cavity comprises sufficient dimensions to accommodate a guest anion.

4. The redox-active triangular prism of claim 1 , wherein structure is stabilized through π-π interactions among adjacent members of the plurality of pure enantiomers upon binding a guest anion.

5. The redox-active triangular prism of claim 1 , wherein the structure comprises a redox activity of greater than two reversible one-electron cathodic waves.

6. The redox-active triangular prism of claim 1 , wherein the plurality of pure enantiomers consist of (−)-NDI-Δ.

7. The redox-active triangular prism of claim of claim 6 , wherein the plurality of pure enantiomers form a structure having a central cavity, wherein the structure is selected from a group consisting of a right-handed, supramolecular (P)-helix, an organogel, a non-helical supramolecular nanotube and a (P)-helical supramolecular nanotube.

8. The redox-active triangular prism of claim of claim 6 , wherein the structure is an organogel comprising a plurality of intertwining supramolecular nanotubes.

9. The redox-active triangular prism of claim 1 , wherein the plurality of pure enantiomers consist of (+)-NDI-Δ.

10. The redox-active triangular prism of claim 9 , wherein the plurality of pure enantiomers form a structure having a central cavity, wherein the structure is selected from a group consisting of a left-handed, supramolecular (M)-helix and a (M)-helical supramolecular nanotube.

11. A method of making a redox-active triangular prism, comprising:
preparing a mixture comprising naphthalene-tetracarboxylic dianhydride, a pure enantiomer selected from a group consisting of (RR)-trans-1,2-cyclohexanediamine and (SS)-trans-1,2-cyclohexanediamine and a solvent; and
incubating the mixture at a temperature above ambient temperature, wherein the redox-active triangular prism formed is a member selected from a group consisting of the following:

12. The method of claim 11 , wherein the solvent comprises an organic solvent.

13. The method of claim 12 , wherein the organic solvent comprises dimethylformamide.

14. The method of claim 11 , wherein the pure enantiomer consists of (RR)-trans-1,2-cyclohexanediamine and the redox-active triangular prism formed is the following:

15. The method of claim 14 , further comprising:
purifying (−)-NDI-Δ product by chromatography; and
precipitating (−)-NDI-Δ.

16. The method of claim 15 , further comprising:
preparing a solution comprising (−)-NDI-Δ and a solvent; and
diffusing n-hexane in the solution to form complexes comprising solvent and (−)-NDI-Δ.

17. The method of claim 16 , wherein the solvent is selected from a group consisting of (E)-1,2-dichloroethene, BrCH 2 CH 2 Br, ClCH 2 CH 2 Br, ClCH 2 CH 2 I and ClCH 2 CH 2 Cl.

18. The method of claim 11 , wherein the pure enantiomer consists of (SS)-trans-1,2-cyclohexanediamine and the redox-active triangular prism formed is the following:

19. The method of claim 18 , further comprising:
purifying (+)-NDI-Δ product chromatography over silica gel; and
precipitating (+)-NDI-Δ.

20. The method of claim 19 , further comprising:
preparing a solution comprising (+)-NDI-Δ and solvent; and
diffusing n-hexane in the solution to form complexes comprising solvent and (+)-NDI-Δ.

21. The method of claim 20 , wherein the solvent is selected from a group consisting of (E)-1,2-dichloroethene, BrCH 2 CH 2 Br, ClCH 2 CH 2 Br, ClCH 2 CH 2 I and ClCH 2 CH 2 Cl.

22. An electrode comprising a redox-active triangular prism, wherein the redox-active triangular prism comprises:
a plurality of pure enantiomers selected from a group consisting of the following:

or a solvent-crystalline complex thereof.

Assignees

• Univ Northwestern
• King Abdulaziz City For Science And Tech (Kacst)

Inventors

• Stoddart James Fraser
• Schneebeli Severin T
• Liu Zhichang
• Frasconi Marco

Classifications

• C07D471/06 Primary

  Peri-condensed systems · CPC title

• C07B2200/13

  Crystalline forms, e.g. polymorphs · CPC title

• C07D471/22 Primary

  in which the condensed systems contains four or more hetero rings · CPC title