Contents 1. Introduction 718 2. Versatile Syntheses of 2D Graphene Molecules 720 2.1. Hexa-peri-hexabenzocoronenes 720 2.2. Larger Graphenes 724 2.3. Chemical Modification of Hexa-peri-hexabenzocoronenes 728 3. Thermotropic Behavior of Graphene Molecules in the Bulk 731 4. Alignment of Graphene Molecules in Thin Films and Their Device Applications 734 5. Self-assembly at Solid−Liquid Interfaces 740 6. Novel Carbonaceous Nanostructures by Solid-State Pyrolysis 742 7. Conclusion and Outlook 744 8. Acknowledgments 745 9. References 745

Chemically modified graphene and polyaniline (PANI) nanofiber composites were prepared by in situ polymerization of aniline monomer in the presence of graphene oxide under acid conditions. The obtained graphene oxide/PANI composites with different mass ratios were reduced to graphene using hydrazine followed by reoxidation and reprotonation of the reduced PANI to give the graphene/PANI nanocomposites. The morphology, composition, and electronic structure of the composites together with pure polyaniline fibers (PANI-F), graphene oxide (GO), and graphene (GR) were characterized using X-ray diffraction (XRD), solid-state 13 C NMR, FT-IR, scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). It was found that the chemically modified graphene and the PANI nanofibers formed a uniform nanocomposite with the PANI fibers absorbed on the graphene surface and/or filled between the graphene sheets. Such uniform structure together with the observed high conductivities afforded high specific capacitance and good cycling stability during the charge-discharge process when used as supercapacitor electrodes. A specific capacitance of as high as 480 F/g at a current density of 0.1 A/g was achieved over a PANI-doped graphene composite. The research data revealed that high specific capacitance and good cycling stability can be achieved either by doping chemically modified graphenes with PANI or by doping the bulky PANIs with graphene/graphene oxide.

Aromaticity is an important concept to understand the stability and physical properties of π-conjugated molecules. Recent studies on pro-aromatic and anti-aromatic molecules revealed their irresistible tendency to become diradicals in the ground state. Diradical character thus becomes another very important concept and it is fundamentally correlated to the physical (optical, electronic and magnetic) properties and chemical reactivity of most of the organic optoelectronic materials. Molecules with distinctive diradical character show unique properties which are very different from those of traditional closed-shell π-conjugated systems, and thus they have many potential applications in organic electronics, spintronics, non-linear optics and energy storage. This critical review first introduces the fundamental electronic structure of Kekulé diradicals within the concepts of anti-aromaticity and pro-aromaticity in the context of Hückel aromaticity and diradical character. Then recent research studies on various stable/persistent diradicaloids based on pro-aromatic and anti-aromatic compounds are summarized and discussed with regard to their synthetic chemistry, physical properties, structure-property relationships and potential material applications. A summary and personal perspective is given at the end.