Functional Graphenic Materials Via a Johnson−Claisen Rearrangement
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ClaisenGO_July17_AFM.pdf
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3.39 MB
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Checksum (MD5)
3b8e947aca07516ab29df3386328b9b1
Author(s)
Sydlik, Stefanie Arlene
Swager, Timothy M
Date Issued
November 2012
Journal
Advanced Functional Materials
Publisher
Wiley Blackwell
Citation
Sydlik, Stefanie A., and Timothy M. Swager. “Functional Graphenic Materials Via a Johnson−Claisen Rearrangement.” Advanced Functional Materials 23, no. 15 (April 19, 2013): 1873-1882.
Version
Author's final manuscript
Abstract
Current research in materials has devoted much attention to graphene, with a considerable amount of the chemical manipulation going through the oxidized state of the material, known as graphene oxide (GO). In this report, the hydroxyl functionalities in GO, the vast majority that must be allylic alcohols, are subjected to Johnson−Claisen rearrangement conditions. In these conditions, a [3, 3] sigmatropic rearrangement after reaction with triethyl orthoacetate gives rise to an ester functional group, attached to the graphitic framework via a robust C−C bond. This variation of the Claisen rearrangement offers an unprecedented versatility of further functionalizations, while maintaining the desirable properties of unfunctionalized graphene. The resultant functional groups were found to withstand reductive treatments for the deoxygenation of graphene sheets and a resumption of electronic conductivity is observed. The ester groups are easily saponified to carboxylic acids in situ with basic conditions, to give water-soluble graphene. The ester functionality can be further reacted as is, or the carboxylic acid can easily be converted to the more reactive acid chloride. Subsequent amide formation yields up to 1 amide in 15 graphene carbons and increases intergallery spacing up to 12.8 Å, suggesting utility of this material in capacitors and in gas storage. Other functionalization schemes, which include the installation of terminal alkynes and dipolar cycloadditions, allow for the synthesis of a highly positively charged, water-soluble graphene. The highly negatively and positively charged graphenes (zeta potentials of −75 mV and +56 mV, respectively), are successfully used to build layer-by-layer (LBL) constructs.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Koch Institute for Integrative Cancer Research at MIT
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Creative Commons Attribution-Noncommercial-Share Alike 3.0
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DOI of Published Version
https://doi.org/10.1002/adfm.201201954
