www.pubs.acs.org/accounts Vol. XXX, No. XX ’ XXXX ’ 000–000 ’ ACCOUNTS OF CHEMICAL RESEARCH ’ A 10.1021/ar300177q & XXXX American Chemical Society Effect of Covalent Chemistry on the Electronic Structure and Properties of Carbon Nanotubes and Graphene ELENA BEKYAROVA, †, ‡ SANTANU SARKAR, †, ‡ FEIHU WANG, †,§ MIKHAIL E. ITKIS, †, ‡ IRINA KALININA, †, ‡ XIAOJUAN TIAN, †, ) AND ROBERT C. HADDON* , †, ^ † Center for Nanoscale Science & Engineering, ‡ Department of Chemistry, § Department of Physics and Astronomy, and ) Department of Chemical & Environmental Engineering, University of California, Riverside, California 92521, United States, and ^ Department of Physics, King Abdulaziz University, Jeddah 21589, Saudi Arabia RECEIVED ON JUNE 15, 2012 CONSPECTUS I n 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) DielsÀAlder pericyclic reactions, and (3) organometallic complexation with transition metals. We provide a unified treat- ment 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 DielsÀAlder 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 σ-bond and the creation of a π-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 (η 6 -SWNT)Cr(η 6 -SWNT), interconnects adjacent graphitic surfaces and significantly reduces the internanotube junction resistance in single-walled carbon nanotube (SWNT) networks. The conversion of sp 2 hybridized carbon atoms to sp 3 can introduce a band gap into graphene, influence the electronic scattering, and create dielectric regions in a graphene wafer. However, the organometallic hexahapto (η 6 ) functionalization of the two-dimensional (2D) graphene π-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 π-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. 1. Introduction In 2004, it became clear that graphene and silicon share a number of features À acceptable mobilities (μ g 1000 cm 2 /V s) 1,2 were evident in the first papers, but another important characteristic was the availability of graphene wafers and this motivated the idea that it might be possible to design and build integrated circuits starting from a graphene wafer, just as the electronics industry does today