Adv Polym Sci (2013) 262: 61–92
DOI: 10.1007/12_2013_239
© Springer-Verlag Berlin Heidelberg 2013
Published online: 29 October 2013
Graphene as a Target for Polymer Synthesis
Klaus Mu ¨llen
Abstract Graphene has remarkable physical properties, but existing production
methods have severe deficiencies that limit its potential use in robust technologies.
Opening a reliable and efficient synthetic route to graphene and its functionalized
derivatives offers a path to overcome this obstacle for its practical application.
Graphene can be regarded as a two-dimensional polymer (2D), and it is here argued
that it, along with its derivatives, represents a realistic yet challenging target for
polymer synthesis.
In order to demonstrate the possibility of such syntheses, an overview is
presented on the evolution of phenylene-based macromolecules. It is shown how
classical linear polyphenylenes can be expanded to increasingly more sophisticated
structures involving two- and three-dimensional (3D) polyphenylene architectures.
A crucial aspect of the meticulous synthetic design of these molecules has been
the avoidance of defects within the structures, resulting in the precise control of
their physical, especially optoelectronic, properties.
Linear conjugated polymers with defined optical properties have been made
by controlling the degree of torsion between the benzene rings. This has included
the development of efficient routes to ladder-type polymers and of step-ladder
materials. Planar graphene molecules, or nanographenes, in a range of sizes and
shapes have been fabricated by the controlled cyclodehydrogenation of 3D polyphenylene dendrimers. By combining knowledge gained from the synthesis of
conjugated polymers, polyphenylene dendrimers, and nanographenes, it has proven
feasible to make, either by solution or surface-bound methods, graphene nanoribbons with well-defined structures. These functional materials possess properties
similar to graphene while displaying improved processability.
Finally, we review less-sophisticated paths towards graphene materials involving
processing of graphene oxide, its reduction, and its hybridization with other
components. These too have a role to play in acquiring functional graphenes where
K. Mu ¨llen (*)
Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
e-mail: muellen@mpip-mainz.mpg.de
DOI: 10.1007/12_2013_239
© Springer-Verlag Berlin Heidelberg 2013
Published online: 29 October 2013
Graphene as a Target for Polymer Synthesis
Klaus Mu ¨llen
Abstract Graphene has remarkable physical properties, but existing production
methods have severe deficiencies that limit its potential use in robust technologies.
Opening a reliable and efficient synthetic route to graphene and its functionalized
derivatives offers a path to overcome this obstacle for its practical application.
Graphene can be regarded as a two-dimensional polymer (2D), and it is here argued
that it, along with its derivatives, represents a realistic yet challenging target for
polymer synthesis.
In order to demonstrate the possibility of such syntheses, an overview is
presented on the evolution of phenylene-based macromolecules. It is shown how
classical linear polyphenylenes can be expanded to increasingly more sophisticated
structures involving two- and three-dimensional (3D) polyphenylene architectures.
A crucial aspect of the meticulous synthetic design of these molecules has been
the avoidance of defects within the structures, resulting in the precise control of
their physical, especially optoelectronic, properties.
Linear conjugated polymers with defined optical properties have been made
by controlling the degree of torsion between the benzene rings. This has included
the development of efficient routes to ladder-type polymers and of step-ladder
materials. Planar graphene molecules, or nanographenes, in a range of sizes and
shapes have been fabricated by the controlled cyclodehydrogenation of 3D polyphenylene dendrimers. By combining knowledge gained from the synthesis of
conjugated polymers, polyphenylene dendrimers, and nanographenes, it has proven
feasible to make, either by solution or surface-bound methods, graphene nanoribbons with well-defined structures. These functional materials possess properties
similar to graphene while displaying improved processability.
Finally, we review less-sophisticated paths towards graphene materials involving
processing of graphene oxide, its reduction, and its hybridization with other
components. These too have a role to play in acquiring functional graphenes where
K. Mu ¨llen (*)
Max-Planck-Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
e-mail: muellen@mpip-mainz.mpg.de