Donor-acceptor nanohoop compounds and methods of making and using the same

1. A compound having a structure satisfying a formula

wherein each D ring independently is selected from phenyl, pyridinyl, benzo[1,2-b:4,5-b′]dithiophenyl; benzo[1,2-b:4,5-b′]difuranyl; or 1,5-dihydropyrrolo[2,3-f]indolyl; and each D ring is connected to other rings of the compound in a para-substitution pattern;

each A ring independently is phenyl, pyridinyl, pyridinyl comprising an aliphatic-substituted nitrogen atom, benzo[c][1,2,5]thiadiazolyl, benzo[c][1,2,5]oxadiazolyl, or 2H-benzo[d][1,2,3]triazolyl; and each A ring is connected to other rings of the compound in a para-substitution pattern;

each “EDG” independently is selected from alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, aliphatic, or aryl;

each “EAG” independently is selected from sulfonate; pyridinyl; alkyl halide; cyano; quaternary amine; nitro; aldehyde; ketone; carboxylic acid; —C(O)R b , wherein R b is selected from alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl; or acyl halide;

each q independently is an integer selected from 0, 1, or 2;

each r independently is an integer selected from 0, 1, or 2;

n is an integer selected from 0 to 18;

m is an integer selected from 0 to 18;

p is an integer selected from 1 to 10; provided that the compound comprises a total number of rings ranging from 6 to 20; and

wherein the compound is not, or is other than,

wherein the compound is not, or is other than, a non-functionalized nanohoop consisting of phenyl rings; and

wherein the compound is not, or is other than, a compound consisting of phenyl and pyridinyl rings, wherein any pyridinyl ring lacks N-substitution with an aliphatic group.

2. The compound of claim 1 , wherein the D ring is phenyl.

3. The compound of claim 1 , wherein each EAG independently is selected from cyano, alkyl halide, pyridinyl, or combinations thereof.

4. The compound of claim 1 , wherein the compound has a structure satisfying any one or more of the following formulas:

wherein

one of a, b, c, or d is carbon, nitrogen, or nitrogen comprising an aliphatic group and each other a, b, c, or d is carbon;

each n′ independently is an integer selected from 1 to 18.

5. The compound of claim 1 , wherein the compound has a structure satisfying a formula

wherein (i) one of a, b, c, or d is carbon and further wherein the A ring comprises one or more electron-accepting groups selected from sulfonate; pyridinyl; alkyl halide; cyano; quaternary amine; nitro; aldehyde; ketone; carboxylic acid; —C(O)R b , wherein R b is selected from akyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl; or acyl halide; and each other a, b, c, or d is carbon; or (ii) one of a, b, c, or d is nitrogen comprising an aliphatic group and each other a, b, c, or d is carbon.

6. The compound of claim 1 , wherein the compound has a structure satisfying a formula selected from

wherein the A phenyl ring comprises one or more electron-accepting groups selected from sulfonate;

pyridinyl; alkyl halide; cyano; quaternary amine; nitro; aldehyde; ketone; carboxylic acid; —C(O)R b, wherein R b is selected from alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl; or acyl halide; and the D phenyl ring comprises one or two EDGs.

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

wherein R 1 is selected from alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, heteroaryl, or hydrogen.

8. The compound of claim 1 , wherein the compound is a functionalized nanohoop compound that exhibits a LUMO energy level ranging from greater than −2.0 eV to −5 eV.

9. The compound of claim 1 , wherein the compound is a functionalized nanohoop compound that exhibits a LUMO energy level ranging from −2.5 eV to −4.0 eV.

10. The compound of claim 1 , wherein the compound is a functionalized nanohoop compound that exhibits a HOMO energy level ranging from −5.0 eV to −7 eV.

11. The compound of claim 1 , wherein the compound is a functionalized nanohoop compound that exhibits a HOMO energy level ranging from −5.2 eV to −6.5 eV.

12. A device, comprising a compound according to claim 1 , wherein the device is an organic photovoltaic device, an organic field effect transistor, a molecular wire, or an organic light emitting diode.

13. A method of making a compound of claim 1 , comprising exposing a compound of a formula

to a reducing agent to thereby produce the compound of claim 1 .

14. The method of claim 13 , wherein the reducing agent is an organic salt.

15. The method of claim 13 , wherein the reducing agent is a metal naphthalenide.

16. The method of claim 13 , wherein the reducing agent is sodium naphthalenide.

17. The compound of claim 1 , wherein each D ring independently is phenyl, pyridinyl, benzo[1,2-b:4,5-b′]dithiophenyl; benzo[1,2-b:4,5-b′]difuranyl; or 1,5-dihydropyrrolo[2,3-f]indolyl; and each A ring independently is a phenyl ring comprising one or two EAGs, or pyridinyl comprising an aliphatic-substituted nitrogen atom.

18. The compound of claim 1 , wherein:

each D ring independently is benzo[1,2-b:4,5-b′]dithiophenyl; benzo[1,2-b:4,5-b′]difuranyl; 1,5-dihydropyrrolo[2,3-f]indolyl; or 4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene; and

each A ring independently is benzo[c][1,2,5]thiadiazolyl, benzo[c][1,2,5]oxadiazolyl, or 2H-benzo[d][1,2,3]triazolyl.

19. The compound of claim 1 , wherein:

each D ring independently is benzo[1,2-b:4,5-b′]dithiophenyl; benzo[1,2-b:4,5-b′]difuranyl; or 1,5-dihydropyrrolo[2,3-f]indolyl; and

each A ring independently is phenyl or pyridinyl comprising an aliphatic-substituted nitrogen atom; or wherein

each D ring independently is selected from phenyl, pyridinyl, benzo[1,2-b:4,5-b′]dithiophenyl; benzo[1,2-b:4,5-b′]difuranyl; or 1,5-dihydropyrrolo[2,3-f]indolyl; and

each A ring independently is benzo[c][1,2,5]thiadiazolyl, benzo[c][1,2,5]oxadiazolyl, or 2H-benzo[d][1,2,3]triazolyl.

20. A compound having a structure satisfying a formula

wherein each D ring independently is a phenyl ring and each D ring is connected to other rings of the compound in a para-substitution pattern;

each A ring independently is a pyridinyl ring comprising a nitrogen atom that is substituted with an aliphatic group and each A ring is connected to other rings of the compound in a para-substitution pattern;

each “EDG” independently is selected from alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, aliphatic, or aryl;

each “EAG” independently is selected from sulfonate; pyridinyl; alkyl halide; cyano; quaternary amine; nitro; aldehyde; ketone; carboxylic acid; —C(O)R b, wherein R b is selected from alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl; or acyl halide;

each q independently is an integer selected from 0, 1, or 2;

each r independently is an integer selected from 0, 1, or 2;

n is an integer selected from 0 to 18;

m is an integer selected from 0 to 18;

p is an integer selected from 1 to 10; provided that the compound comprises a total number of rings ranging from 6 to 20; and

wherein the compound is not, or is other than,

21. A compound having a structure satisfying a formula

wherein

each D ring independently is 4,4-dimethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene; and each D ring is connected to other rings of the compound in a para-substitution pattern;

each A ring independently is phenyl, pyridinyl, pyridinyl comprising an aliphatic-substituted nitrogen atom, benzo[c][1,2,5]thiadiazolyl, benzo[c][1,2,5]oxadiazolyl, or 2H-benzo[d][1,2,3]triazolyl; and each A ring is connected to other rings of the compound in a para-substitution pattern;

each “EDG” independently is selected from alkoxy, thioether, amide, amine, hydroxyl, thiol, acyloxy, aliphatic, or aryl;

each “EAG” independently is selected from sulfonate; pyridinyl; alkyl halide; cyano; quaternary amine; nitro; aldehyde; ketone; carboxylic acid; —C(O)R b, wherein R b is selected from alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroalkenyl, heteroalkynyl, or heteroaryl; or acyl halide;

each q independently is an integer selected from 0, 1, or 2;

each r independently is an integer selected from 0, 1, or 2;

n is an integer selected from 0 to 18;

m is an integer selected from 0 to 18; and

p is an integer selected from 1 to 10; provided that the compound comprises a total number of rings ranging from 6 to 20.