Quinolines, polyquinolines, molecular segments of fullerenes and graphene nanoribbons, and graphene nanoribbons and methods of their synthesis

Patent metadata

Field	Value
Publication number	US-10899711-B2
Application number	US-201515538180-A
Country	US
Kind code	B2
Filing date	Dec 31, 2015
Priority date	Dec 31, 2014
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

Abstract

Quinolines, polyquinolines, polybenzoquinolines, molecular segments of fullerenes and graphene nanoribbons, and graphene nanoribbons and processes for producing such materials are provided. The processes utilize a form of an aza-Diels-Alder (Povarov) reaction to first form quinolines and/or polyquinolines. In some such embodiments polyquinolines thus produced are used to form graphene nanoribbon precursors, and molecular segments and graphene nanoribbons. In many such embodiments the graphene nanoribbon precursors are formed from polybenzoquinolines.

First claim

What is claimed is:

1. A method of producing bi-quinolines or polyquinolines comprising:
reacting a bifunctional aromatic aldimine with an aromatic mono- or bialkynyl in the presence of a Lewis acid mediator and an oxidant to produce the corresponding bi-quinoline or polyquinoline, wherein:
the bifunctional aromatic aldimine is of formula:

comprising:
a first aromatic core comprising aromatic or heteroaromatic rings,
wherein
n is a number of distinct rings and is an integer of at least 1, and
the first aromatic core is optionally substituted with one or more functionalities each independently selected from the group: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, or any combination thereof;

a first aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R1 is an aromatic or heteroaromatic functionality optionally substituted with one or more substituents, each independently selected from the group: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, a nitrate, a nitrile, another electron withdrawing or electron donating functionality, or any combination thereof; and

a second aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R2 is one of the functionalities selected from the group of: R1, a substituted aromatic ring, an unsubstituted aromatic ring, a substituted heteroaromatic ring, and an unsubstituted heteroaromatic ring; and

the aromatic mono- or bialkynyl comprises a second aromatic core and one or two aromatic terminal alkyne functionalities respectively; and wherein

the first and the second aldimine functionalities of the bifunctional aromatic aldimine react with the one or two aromatic terminal alkyne functionalities of the aromatic mono- or bialkynyl to yield the corresponding bi-quinoline or polyquinoline comprising quinoline moieties incorporating the nitrogens of the first and the second aldimine functionalities.

2. The method of claim 1 , wherein n is 2 such that the first aromatic core is a naphthyl and the quinoline moieties are benzoquinoline.

3. The method of claim 1 , wherein n is 2 and the ring that does not bear the first aldimine functionality is heteroaromatic.

4. The method of claim 3 , wherein the heteroaromatic ring is a pyridine-type and the quinoline moieties are of the phenanthroline variant.

5. The method of claim 2 , wherein the first aldimine functionality is attached at position 1 of the naphthyl, and the naphthyl is further functionalized at position 8 with at least one of: aliphatic group, electron withdrawing group, electron donating group.

6. The method of claim 1 , wherein n is at least 2 and some or all of the aromatic rings of the first aromatic core are linked at the 4 and 6 positions rather than fused, such that the aromaticity of the first aromatic core is maintained.

7. The method of claim 1 , wherein the second aromatic core is a naphthyl moiety.

8. The method of claim 7 , wherein the naphthyl moiety is substituted with one or more substituents, each independently selected from the group: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, a nitrate, a nitrile, another electron withdrawing or electron donating functionality, or any combination thereof.

9. The method of claim 1 , wherein both the aromatic monoalkynyl comprising one aromatic terminal alkyne functionality and the aromatic bialkynyl comprising two aromatic alkyne functionalities are used in the same reaction mixture to control the length of the polyquinolines.

10. A method of forming nitrogen-doped aromatic molecular segments or graphene nanoribbons comprising:
reacting a bifunctional aromatic aldimine with an aromatic mono- or bialkynyl in the presence of a Lewis acid mediator and an oxidant to produce the corresponding bi-quinoline or polyquinoline, and
forming intramolecular C—C bonds between aromatic and heteroaromatic moieties of the corresponding bi-quinoline or polyquinoline to form the corresponding nitrogen-doped molecular segment or graphene nanoribbon, wherein:
the bifunctional aromatic aldimine is of formula:

comprising:
a first aromatic core comprising aromatic or heteroaromatic rings,
wherein
n is a number of distinct rings and is an integer of at least 1, and
the first aromatic core is optionally substituted at any of its aromatic or heteroaromatic rings with one or more functionalities each independently selected from the group: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, or any combination thereof;

a first aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R1 is an aromatic or heteroaromatic functionality optionally substituted with one or more substituents, each independently selected from the group: a halogen, an alkyl, an alkoxy, an acetyl, an N-acetyl, an amine, an alkyl amine, a sulfide, a nitrate, a nitrile, another electron withdrawing or electron donating functionality, or any combination thereof; and

a second aldimine functionality immediately and covalently attached to the first aromatic core, wherein
R2 is one of the functionalities selected from the group of: R1, a substituted aromatic ring, an unsubstituted aromatic ring, a substituted heteroaromatic ring, and an unsubstituted heteroaromatic ring; and

the aromatic mono- or bialkynyl comprises a second aromatic core, and one or two aromatic terminal alkyne functionalities, respectively; and wherein
the first and the second aldimine functionalities of the bifunctional aromatic aldimine react with the one or two aromatic terminal alkyne functionalities of the aromatic mono- or bialkynyl to yield the corresponding bi-quinoline or polyquinoline comprising quinoline moieties incorporating the nitrogens of the first and the second aldimine functionalities.

11. The method of claim 10 , wherein n is 1, the first aromatic core is a benzene additionally substituted with two Cl functionalities at positions 2 and 5, the second aldimine functionality is located at position 4, the aromatic monoalkynyl is phenylacetylene, and two intramolecular CC bonds are formed via Heck reaction such that the corresponding nitrogen-doped molecular segment or graphene nanoribbon is a rubicene nitrogen-doped molecular segment.

12. The method of claim 10 , wherein n is 1, the first aromatic core is a benzene additionally substituted with two Cl functionalities at positions 2 and 5, the second aldimine functionality is located at position 4, the aromatic monoalkynyl is naphthyl alkyne, and two intramolecular C—C bonds are formed via base mediated cyclodehydrogenation reaction such that the corresponding nitrogen-doped molecular segment or graphene nanoribbon is a tetrabenzopentacene nitrogen-doped molecular segment.

13. The method of claim 10 , wherein the aromatic bialkynyl is 1,5-dichloro-9,10-diethynylanthracene, and intramolecular C—C bonds are formed via Heck reaction.

14. The method of claim 10 , wherein the aromatic bialkynyl is 1,5-dichloro-9,10-diethynylanthracene, and intramolecular C—C bonds are formed via base mediated cyclodehydrogenation reaction.

15. A bifunctional aromatic aldimine for producing quinolines, polyquinoli

Assignees

• Univ California

Inventors

• Gorodetsky Alon
• Dibble David Joshua
• Umerani Mehran
• Mazaheripour Amir
• Park Young Suk
• Burke Anthony

Classifications

• C07D215/18

  Halogen atoms or nitro radicals · CPC title

• C07D221/12

  Phenanthridines · CPC title

• C07D215/04

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms · CPC title

• C08L79/02

  Polyamines · CPC title

• C07D401/14

  containing three or more hetero rings · CPC title