In this Account, we discuss the chemistry of graphitic materials with particular reference to three reactions studied by our research group: (1) aryl radical addition, from diazonium precursors, (2) Diels-Alder pericydic reactions, and (3) organometallic complexation with transition metals. We provide a unified treatment of these reactions In terms of the degenerate valence and conduction bands of graphene at the Dirac point and the relationship of their orbital coefficients to the HOMO and LUMO of benzene and to the Clar structures of graphene. In the case of the aryl radical addition and the Diels-Alder reactions, there Is full rehybridization of the derivatized carbon atoms in graphene from sp(2) to sp(3), which removes these carbon atoms from conjugation and from the electronic band structure of graphene (referred to as destructive rehybridization). The radical addition process requires an electron transfer step followed by the formation of a sigma-bond and the creation of a pi-radical in the graphene lattice, and thus, there is the potential for unequal degrees of functionalization in the A and B sublattices and the possibility of ferromagnetism and superparamagnetism in the reaction products. With regard to metal functionalization, we distinguish four limiting cases: (a) weak physisorption, (b) ionic chemisorption, in which there is charge transfer to the graphitic structure and preservation of the conjugation and band structure, (c) covalent chemisorption, in which there is strong rehybridization of the graphitic band structure, and (d) covalent chemisorption with formation of an organometallic hexahapto-metal bond that largely preserves the graphitic band structure (constructive rehybridization). The constructive rehybridization that accompanies the formation of bis-hexahapto-metal bonds, such as those in (eta(6)-SWNT)Cr(eta(6)-SWNT), interconnects adjacent graphitic surfaces and significantly reduces the intemanotube junction resistance in single-walled carbon nanotube (SWNT) networks. The conversion of sp2 hybridized carbon atoms to sp3 can introduce a band gap into graphene, influence the electronic scattering, and create dielectric regions in a graphene wafer. However, the organometallic hexahapto (eta(6)) functionalization of the two-dimensional (2D) graphene pi-surface with transition metals provides a new way to modify graphitic structures that does not saturate the functionalized carbon atoms and, by preserving their structural integrity, maintains the delocalization in these extended periodic pi-electron systems and offers the possibility of three-dimensional (3D) interconnections between adjacent graphene sheets. These structures may find applications In Interconnects, 3D-electronics, organometallic catalysis, atomic spintronics and in the fabrication of new electronic materials.
