Synthesis Of Anilino-Chlorinated Nanographene And Its Supramolecular Assembly

Since 1985,carbon allotropes such as fullerenes,carbon nanotubes and graphene have been discovered and studied.Because of their unique structures and properties,they have lots of applications in optics,electricity,magnetism and other aspects.Among them,graphene has been highly attentions in recent decades.However,due to the uncertainty’s chemical reactions and lacking of effective characterization methods,it is still a difficult problem that precisely synthesized functional graphene.Nanographene,which is a larger than 1 nm graphene-like molecule,has many advantages in characterization due to its defined structure.It has excellent photoelectric properties,being a model of graphene and promising potential applications.Peripheral functionalization of nanographene can modulate its HOMO-LUMO gap,which would be applied to spotlight fields such as solar cells,lithium ion batteries,supramolecular assembly.However,the study of peripheral functionalization of nanographene is very difficult because of its excessive reaction sites and poor solubility.This dissertation contributes from two aspects:new approach to synthesize peripheral functional nanographene and supramolecular assemblies of nanographene.The first section of dissertation,anilino-chlorinated nanographenes have been synthesized.Electron-deficient perchlorinated nanographenes are shown to furnish a series of "reversed" donor-acceptor structures by a regioselective C-N Buchwald-Hartwig coupling with electron-rich anilines.Regioselective amination at the six vertexes of the nanographene was unambiguously proven through X-ray crystallography.By varying the donating ability of the anilino groups,the optical and electronic properties of donor-acceptor nanographenes could be finely modulated.The second section of dissertation,supramolecular assembly of anilino chlorinated nanographenes with tetrathiafulvalene and fullerene have been studied.The electron-deficient concave core of the conjugated nanographenes can host electron-rich guest molecule,tetrathiafulvalene,by intermolecular donor-acceptor interactions and give rise to charge-transfer supramolecular architectures.Also,the electron-rich peripharal functional group,anilines,can interact with electron-deficient molecule,fullerene.Both supramolecular assembly structure was vertified by X-ray crystallography.1 he third section of dissertation,supramolecular asserubly of anilino-chlorinated nanographene with buckybowls have been studied.Two different curved supramolecular assmebly was seldom observed in the past research.Trithiasumanene and nanographene which have their own irrelative curved molecules,interact with each other proven through X-ray crystallography and 1H NMR.With the deeper understanding the mechianism of this supramolecular behavior,three-component co-crystal were observed when added the fullerene molecule.The fourth section of dissertation,bowl inversion in the solid state have been studied.Bowl-shaped geometry of buckybowls leads to their unique bowl inversion.The inversion of buckybowls is still not observed in the crystaline state.By modulating Tuning the electronic deficiency of nanogaphene,the bowl inversion of trithiasumanene in solid is realized by varying temperature,which was unambiguously characterized by X-ray crystallography.