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

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.

A bifunctional aromatic aldimine for producing quinolines, polyquinolines, nitrogen-doped aromatic molecular segments, and graphene nanoribbons according to:

• and comprising:
• an 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 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;
• an aldimine functionality immediately and covalently attached to the aromatic core, wherein R is a substituted or unsubstituted aromatic or heteroaromatic ring;
• and
• an aromatic terminal alkyne functionality immediately and covalently attached at any position of the aromatic core and capable of reacting with an aromatic aldimine in an aza-Diels Alder Povarov reaction.

A method of producing polyquinolines comprising:

• reacting a bifunctional aromatic aldimine with itself in the presence of a Lewis acid mediator and an oxidant to produce the corresponding polyquinoline, wherein:
• the bifunctional aromatic aldimine is of formula:
• comprising:
• an 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 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;
• an aldimine functionality immediately and covalently attached to the aromatic core, wherein
• R 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
• an aromatic terminal alkyne functionality immediately and covalently attached at any position of the aromatic core;
• and wherein
• the aldimine functionality of one molecule of the bifunctional aromatic aldimine reacts with the aromatic terminal alkyne functionality of another molecule of the bifunctional aromatic aldimine to yield the corresponding polyquinoline comprising quinoline moieties incorporating the nitrogens of the aldimine functionalities.

A method of forming nitrogen-doped graphene nanoribbons comprising:

• reacting a bifunctional aromatic aldimine with itself in the presence of a Lewis acid mediator and an oxidant to produce the corresponding polyquinoline, and
• forming intramolecular C—C bonds between aromatic and heteroaromatic moieties of the corresponding polyquinoline to form the corresponding nitrogen-doped graphene nanoribbon, wherein:
• the bifunctional aromatic aldimine is of formula:
• comprising:
• an 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 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;
• an aldimine functionality immediately and covalently attached to the aromatic core, wherein
• R 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
• an aromatic terminal alkyne functionality immediately and covalently attached to the aromatic core;
• and wherein
• the aldimine functionality of one molecule of the bifunctional aromatic aldimine reacts with the aromatic terminal alkyne functionality of another molecule of the bifunctional aromatic aldimine to yield the polyquinolines comprising quinoline moieties incorporating the nitrogens of the aldimine functionalities.

A method of producing nitrogen-doped graphene segments comprising:

• reacting an aromatic aldimine with an aromatic bialkynyl in the presence of a Lewis acid mediator and an oxidant to produce the corresponding biquinoline;
• and
• forming intramolecular C—C bonds between aromatic and heteroaromatic moieties of the corresponding biquinoline to form the corresponding nitrogen-doped graphene segment, wherein:
• the 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;
• and
• an aldimine functionality attached to the first aromatic core, wherein
• R 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
• the aromatic bialkynyl comprises a second aromatic core and two aromatic terminal alkyne functionalities;
• and
• wherein
• the aldimine functionalities of two molecules of the aromatic aldimine react with the two aromatic terminal alkyne functionalities of one molecule of the aromatic bialkynyl to yield quinoline moieties incorporating the nitrogens of the aldimine functionalities.