Polymer embodiments comprising nanohoop-containing polymer backbones and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-11505644-B2
Application number	US-202017033458-A
Country	US
Kind code	B2
Filing date	Sep 25, 2020
Priority date	Sep 27, 2019
Publication date	Nov 22, 2022
Grant date	Nov 22, 2022

Abstract

Polymer embodiments comprising nanohoop-containing polymer backbones are described, along with methods of making and using the same. The polymer embodiments exhibit unique radial and linear conjugation and can be used in a variety of devices, such as electronic and/or optoelectronic devices.

First claim

We claim:

1. A polymer having a structure according to Formula I

wherein the nanohoop comprises six or more aromatic ring systems and wherein each aromatic ring system is directly bound to at least two other aromatic ring systems of the nanohoop by two separate single covalent bonds positioned para, ortho, or meta relative to one another, wherein one of the two separate single covalent bonds is directly bound to one of the at least two other aromatic ring systems and the other of the separate single covalent bonds is directly bound to the other of the at least two other aromatic ring systems; Ar is an aromatic ring system; and n is an integer selected from 2 or greater.

2. The polymer of claim 1 , wherein each nanohoop is bound to each of the two adjacent alkyne groups of Formula I by two different carbon atoms of a single aromatic ring system of the nanohoop.

3. The polymer of claim 2 , wherein the two different carbon atoms of the single aromatic ring system of the nanohoop are positioned para relative to one another.

4. The polymer of claim 1 , wherein each nanohoop is bound to each of the two adjacent alkyne groups of Formula I by two different carbon atoms of two different aromatic ring systems of the nanohoop, wherein one of the two different carbon atoms is part of one of the two different aromatic ring systems and the other of the two different carbon atoms is part of the other of the two different aromatic ring systems.

5. The polymer of claim 1 , wherein the Ar group is an aryl ring or a heteroaryl ring.

6. The polymer of claim 1 , wherein the Ar group is selected from phenyl, naphthyl, pyridinyl, thiophenyl, furanyl, or imidazoyl.

7. The polymer of claim 1 , wherein n is an integer ranging from 2 to 10,000.

8. The polymer of claim 1 , having a structure according to Formulas IIA or IIB

wherein each A ring independently is an aromatic ring system; each R independently is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group; each of rings B, C, D, E, F, and G independently is an aromatic ring system; each R′ independently is aliphatic, heteroaliphatic, haloaliphatic, aromatic, or an organic functional group; each m independently is an integer selected from 1 to 95; each p independently is an integer selected from 0 to 10; n is an integer selected from 2 or greater; and each q independently is an integer selected from 0 to 10.

9. The polymer of claim 8 , wherein each of rings A, B, C, D, E, F, and G independently is aryl or heteroaryl.

10. The polymer of claim 8 , wherein each A ring is a phenyl ring, furan, thiophene, or pyrrole, and wherein each of rings B, C, D, E, F, and G independently is phenyl.

11. The polymer of claim 8 , wherein p is 2 and each R independently is selected from aliphatic.

12. The polymer of claim 1 , having a structure according to Formulas IIIA, IIIB, IVA′, or IVB′

wherein each R independently is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or an organic functional group; each m independently is an integer selected from 1 to 95; and each p independently is an integer selected from 0 to 10.

13. The polymer of claim 1 , wherein the polymer is selected from

14. The polymer of claim 1 , wherein the polymer is

15. A method, comprising exposing a polymerizable nanohoop monomer to a transition metal catalyst, a copper-containing reagent, a base, and an aromatic coupling partner functionalized with a halogen atom to provide the polymer according to claim 1 ; wherein the polymerizable nanohoop monomer has a structure according to Formula V

wherein the nanohoop of Formula V comprises six or more aromatic ring systems and wherein each aromatic ring system is directly bound to at least two other aromatic ring systems of the nanohoop by two separate single covalent bonds positioned para, ortho, or meta relative to one another, wherein one of the two separate single covalent bonds is directly bound to one of the at least two other aromatic ring systems and the other of the separate single covalent bonds is directly bound to the other of the at least two other aromatic ring systems.

16. The method of claim 15 , wherein the transition metal catalyst is a palladium catalyst, the copper-containing reagent is CuI, the base is an amine base, Cs 2 CO 3 , K 2 CO 3 , or K 3 PO 4 , and the aromatic coupling partner comprises an aryl or heteroaryl ring functionalized with the halogen atom.

17. A compound having a structure according to Formula V or Formula VI for use in making the polymer of claim 1 ,

wherein the nanohoop comprises six or more aromatic ring systems and wherein each aromatic ring system is directly bound to at least two other aromatic ring systems of the nanohoop by two separate single covalent bonds positioned para, ortho, or meta relative to one another, wherein one of the two separate single covalent bonds is directly bound to one of the at least two other aromatic ring systems and the other of the separate single covalent bonds is directly bound to the other of the at least two other aromatic ring systems; Ar is an aromatic ring system; and Y is hydrogen, copper, a palladium complex, or an aromatic ring system; and wherein the compound having a structure according to Formula V or Formula VI reacts to become part of the polymer.

18. The compound of claim 17 , wherein the compound has a structure according to Formula VIIA, VIIB, VIIIA, or VIIIB

wherein each of rings B, C, D, E, F, and G independently is an aromatic ring system; each R′ independently is aliphatic, heteroaliphatic, haloaliphatic, aromatic, or an organic functional group; each m independently is an integer selected from 1 to 95; and each q independently is an integer selected from 0 to 10.

19. The compound of claim 17 , wherein the compound has a structure according to Formula IXA, IXB, XA, or XB

wherein m is 1 or 3.

20. A method, comprising:
coupling a nanohoop intermediate with an aromatic monomer functionalized with an alkyne moiety to provide a non-aromatized nanohoop intermediate; and
exposing the non-aromatized nanohoop intermediate to a reductive aromatization to provide the compound according to claim 17 , w

Assignees

• Univ Oregon
• Univ Johns Hopkins
• Univ Georgetown

Inventors

• Jasti Ramesh
• Maust Ruth
• Colwell Curtis
• Tovar John Dayton
• Peters Garvin
• Bates Haley
• Kertesz Miklos
• Grover Girishma

Classifications

• C08G61/126 Primary

  with a five-membered ring containing one sulfur atom in the ring · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title

• C08G2261/3328

  alkyne-based · CPC title

• C08G2261/42

  Non-organometallic coupling reactions, e.g. Gilch-type or Wessling-Zimmermann type · CPC title