Halogenated nanohoop compounds and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-2018290952-A1
Application number	US-201815900529-A
Country	US
Kind code	A1
Filing date	Feb 20, 2018
Priority date	Apr 11, 2017
Publication date	Oct 11, 2018
Grant date	—

Abstract

Disclosed herein are embodiments of halogenated nanohoop compounds and assemblies thereof that can be used to for a variety of biological and chemical applications. The halogenated nanohoop compounds described herein exhibit non-covalent interactions that promote their ability to stack and form column-like assemblies having uniform pore size and that do not exhibit structural defects typically associated with other column-like structures, such as carbon nanotubes. Assemblies described herein also are capable of non-covalent interactions with other assemblies and thus can be used to form networks of the assemblies described herein.

First claim

We claim:

1 . A compound having a structure satisfying Formula I

wherein each A ring independently is an aromatic ring that does not require a halogen atom;
each X independently is chloro, fluoro, bromo, or iodo;
each R independently is an electron-donating group or an electron-accepting group;
each n, n′, and r independently is an integer selected from 0 to 24;
p is an integer selected from 1-12, provided that when each of n, n′, and r is 0, then p is at least 6, and provided that when p is 1, then at least one of n, n′, or r is 5;
each s and s′ independently is an integer selected from 0 to 4; and
each q and q′ independently is an integer selected from 1 to 4.

2 . The compound of claim 1 , wherein each A ring independently is phenyl ring; a benzo[1,2-b:4,5-b′]dithiophenyl ring; a benzo[1,2-b:4,5-b′]difuranyl ring; a 1,5-dihydropyrrolo[2,3-f]indolyl ring; a pyridinyl ring substituted with an aliphatic or aryl group; a benzo[c][1,2,5]thiadiazolyl ring; a benzo[c][1,2,5]oxadiazolyl ring; or a 2H-benzo[d][1,2,3]triazolyl ring.

3 . The compound of claim 2 , wherein the phenyl ring, the benzo[1,2-b:4,5-b′]dithiophenyl ring, the benzo[1,2-b:4,5-b′]difuranyl ring, the 1,5-dihydropyrrolo[2,3-f]indolyl ring, the benzo[c][1,2,5]thiadiazolyl ring, the benzo[c][1,2,5]oxadiazolyl, ring, and/or the 2H-benzo[d][1,2,3]triazolyl ring is substituted with one or more electron-donating substituents, one or more electron-accepting groups, or a combination thereof;

4 . The compound of claim 3 , wherein the one or more electron-donating substituents is alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, aliphatic, aryl, or combinations thereof.

5 . The compound of claim 3 , wherein the electron-accepting substituents is aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, sulfonate, nitro, nitroso, quaternary amine, alkyl halide, or combinations thereof.

6 . The compound of claim 1 , wherein the A ring independently is 4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene, phenyl, or combinations thereof.

7 . The compound of claim 1 , wherein each X is fluoro.

8 . The compound of claim 1 , wherein q and q′ independently are 1, 2, 3, or 4.

9 . The compound of claim 1 , wherein n′ and r each are 1 and p is 6.

10 . The compound of claim 1 , wherein the compound has a structure satisfying any one or more of Formulas IIA-IIL

11 . The compound of claim 1 , wherein the compound has a structure satisfying any one or more of Formulas IIIA-IIIC

wherein each a, b, c, and d can be selected from carbon or nitrogen and each Y independently can be selected from O, S, or NH.

12 . The compound of claim 1 , wherein the compound is

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

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

15 . The compound of claim 1 , wherein the compound is

16 . An assembly, comprising a plurality of nanohoop compounds that are arranged, through one or more C—H/C—X interactions, in a column-like configuration, wherein at least one of the nanohoop compounds is a compound according to claim 1 .

17 . A device, comprising a halogenated nanohoop compound according to claim 1 , wherein the device is an energy storage device, a nanoreactor, an electronic device, a biological transport device, or a chemical device.

18 . The device of claim 17 , wherein the energy storage device is a capacitor, an electrode, a solar cell, a fuel cell, or a battery.

19 . The device of claim 17 , wherein the electronic device is a two-contact electronic device.

20 . The device of claim 17 , wherein the nanoreactor further comprises one or more guest species.

21 . A method of making a halogenated nanohoop compound, comprising:
cross-coupling a compound having a structure satisfying Formula A with a compound having a structure satisfying Formula C to form a nanohoop precursor having a structure satisfying Formula C; and deprotecting the nanohoop precursor in the presence of acetic acid to form the halogenated nanohoop compound;
wherein
Formula A is

Formula B is

and
Formula C is

and wherein each R′ independently is a silyl protecting group, each A ring independently is aromatic ring that does not require a halogen atom; each R independently is an electron-donating group or an electron-accepting group; each X independently is chloro, fluoro, bromo, or iodo; each s independently is an integer selected from 0 to 4; each q independently is an integer selected from 1 to 4; and each n independently is an integer selected from 0 to 24.

22 . The method of claim 21 , wherein the cross-coupling is performed using a transition metal-based catalyst and a base.

23 . A method of making a halogenated nanohoop compound, comprising:
cross-coupling a compound having a structure satisfying Formula D with a compound having a structure satisfying Formula C to form a nanohoop precursor having a structure satisfying Formula D; and deprotecting the nanohoop precursor in the presence of acetic acid to form the halogenated nanohoop compound;
wherein
Formula D i

Assignees

• Univ Oregon

Inventors

• Jasti Ramesh
• Van Raden Jeff
• Leonhardt Erik

Classifications

• B01J37/22

  Halogenating · CPC title

• H01M4/60

  of organic compounds · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• Y10S977/734

  Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc. · CPC title

• C07C25/18 Primary

  Polycyclic aromatic halogenated hydrocarbons · CPC title