Efficient
and selective methods for covalent derivatization of
graphene are needed because they enable tuning of graphene’s
surface and electronic properties, thus expanding its application
potential. However, existing approaches based mainly on chemistry
of graphene and graphene oxide achieve only limited level of functionalization
due to chemical inertness of the surface and nonselective simultaneous
attachment of different functional groups, respectively. Here we present
a conceptually different route based on synthesis of cyanographene via the controllable substitution and defluorination of
fluorographene. The highly conductive and hydrophilic cyanographene
allows exploiting the complex chemistry of −CN groups toward
a broad scale of graphene derivatives with very high functionalization
degree. The consequent hydrolysis of cyanographene results in graphene
acid, a 2D carboxylic acid with pKa of
5.2, showing excellent biocompatibility, conductivity and dispersibility
in water and 3D supramolecular assemblies after drying. Further, the
carboxyl groups enable simple, tailored and widely accessible 2D chemistry
onto graphene, as demonstrated via the covalent conjugation
with a diamine, an aminothiol and an aminoalcohol. The developed methodology
represents the most controllable, universal and easy to use approach
toward a broad set of 2D materials through consequent chemistries
on cyanographene and on the prepared carboxy-, amino-, sulphydryl-,
and hydroxy- graphenes.