Compositions comprising and methods for forming functionalized carbon-based nanostructures

1. A composition, comprising:

graphene or graphene oxide comprising at least one functional group associated with the graphene or graphene oxide, wherein the at least one functional group has the structure:

wherein R 1 , R 2 , and R 3 are the same or different and each is independently a substituent, optionally substituted; and

G comprises a carbon atom of the graphene or graphene oxide.

2. The composition of claim 1 , wherein:

R 1 and R 2 are the same or different and each is independently hydrogen, alkyl, heteroalkyl, cycloalkyl, alkenyl, or aryl, any of which is optionally substituted.

3. The composition of claim 1 , wherein:

R 3 is hydrogen, alkyl, aryl, alkenyl, cycloalkyl, heteroalkyl, heteroaryl, N(R 4 ) 2 , SR 4 , Si(R 4 ) 2 , OR 4 , or OM, any of which is optionally substituted,

M is a metal or cationic species; and

each R 4 is independently a substituent, optionally substituted.

4. The composition of claim 1 , wherein the functional group comprises an electrochemically active species.

5. The composition of claim 4 , wherein the electrochemically active species is a conducting polymer, metal, semi-metal, or semiconductors.

6. The composition of claim 1 , wherein the functional group is capable of reducing oxygen.

7. The composition of claim 1 , wherein the functional group comprises a ligand for binding one or more metal atoms.

8. The composition of claim 1 , wherein the functional group is capable of associating with and/or storing redox active species.

9. The composition of claim 8 , wherein the redox species is lithium.

10. A method for fabricating a functionalized carbon-based nanostructure, comprising:

providing a carbon-based nanostructure comprising a first allylic functional group;

reacting the carbon-based nanostructure with a reactant comprising at least one carbon atom to transform the first allylic functional group into a second allylic functional group; and

allowing the second allylic functional group to undergo a rearrangement via a sigmatropic rearrangement reaction,

thereby forming a carbon-carbon bond between the at least one carbon atom within the reactant and a carbon atom within the carbon-based nanostructure,

wherein the carbon-based nanostructure is graphene or graphene oxide.

11. The method of claim 10 , wherein the reactant comprising at least one carbon atom is CH 3 C(OCH 3 ) 3 .

12. The method of claim 10 , wherein the reactant comprising at least one carbon atom is an acyl ketene species.

13. The method of claim 10 , wherein the first allylic functional group is positioned on or within the basal plane of the graphene or graphene oxide.

14. The method of claim 10 , further comprising:

treating the carbon-based nanostructure with a reducing agent.

15. A method for fabricating a functionalized carbon-based nanostructure, comprising:

providing a carbon-based nanostructure including a group having the formula (I):

wherein C 1 , C 2 , and C 3 are part of a fused network of aromatic rings within the carbon-based nanostructure and OR 5 is a pendant group of the fused network of aromatic rings, and R 5 is a substituent, optionally substituted; and

reacting the carbon-based nanostructure with a reactant to produce a group having the formula (II):

wherein R 6 , R 7 , and R 8 are the same or different and each is independently a substituent, optionally substituted.

16. The method of claim 15 , wherein the reacting proceeds via an intermediate group having formula (III):

wherein R 9 , R 10 , and R 11 are the same or different and each is independently a substituent, optionally substituted;

or wherein R 9 and R 10 together form ═NR 14 or ═O;

R 14 is a substituent, optionally substituted;

n is 2 or 3; and

represents a single or double bond.

17. The method of claim 16 , wherein the group of formula (III) comprises the structure: