We describe the design and synthesis of a new graphene ribbon architecture that consists of perylenediimide (PDI) subunits fused together by ethylene bridges. We created a prototype series of oligomers consisting of the dimer, trimer, and tetramer. The steric congestion at the fusion point between the PDI units creates helical junctions, and longer oligomers form helical ribbons. Thin films of these oligomers form the active layer in n-type field effect transistors. UV-vis spectroscopy reveals the emergence of an intense long-wavelength transition in the tetramer. From DFT calculations, we find that the HOMO-2 to LUMO transition is isoenergetic with the HOMO to LUMO transition in the tetramer. We probe these transitions directly using femtosecond transient absorption spectroscopy. The HOMO-2 to LUMO transition electronically connects the PDI subunits with the ethylene bridges, and its energy depends on the length of the oligomer.

CONSPECTUS: This Account describes a body of research in the design, synthesis, and assembly of molecular materials made from strained polycyclic aromatic molecules. The strain in the molecular subunits severely distorts the aromatic molecules away from planarity. We coined the term "contorted aromatics" to describe this class of molecules. Using these molecules, we demonstrate that the curved pi-surfaces are useful as subunits to make self-assembled electronic materials. We have created and continue to study two broad classes of these "contorted aromatics": discs and ribbons. The figure that accompanies this conspectus displays the three-dimensional surfaces of a selection of these "contorted aromatics". The disc-shaped contorted molecules have well-defined conformations that create concave pi-surfaces. When these disc-shaped molecules are substituted with hydrocarbon side chains, they self-assemble into columnar superstructures. Depending on the hydrocarbon substitution, they form either liquid crystalline films or macroscopic cables. In both cases, the columnar structures are photoconductive and form p-type, hole- transporting materials in field effect transistor devices. This columnar motif is robust, allowing us to form monolayers of these columns attached to the surface of dielectrics such as silicon oxide. We use ultrathin point contacts made from individual single-walled carbon nanotubes that are separated by a few nanometers to probe the electronic properties of short stacks of a few contorted discs. We find that these materials have high mobility and can sense electron-deficient aromatic molecules. The concave surfaces of these disc-shaped contorted molecules form ideal receptors for the molecular recognition and assembly with spherical molecules such as fullerenes. These interfaces resemble ball-and-socket joints, where the fullerene nests itself in the concave surface of the contorted disc. The tightness of the binding between the two partners can be increased by creating more hemispherically shaped contorted molecules. Given the electronic structure of these contorted discs and the fullerenes, this junction is a molecular version of a p-n junction. These ball-and-socket interfaces are ideal for photoinduced charge separation. Photovoltaic devices containing these molecular recognition elements demonstrate approximately two orders of magnitude increase in charge separation. The ribbon-shaped, contorted molecules can be conceptualized as ultranarrow pieces of graphene. The contortion causes them to wind into helical ribbons. These ribbons can be formed into the active layer of field effect transistors. We substitute the ribbons with di-imides and therefore are able to transport electrons. Furthermore, these materials absorb light strongly and have ideal energetic alignment of their orbitals with conventional p-type electronic polymers. In solar cells, these contorted ribbons with commercial donor polymers have record efficiencies for non-fullerene-based solar cells. An area of interest for future explo...

Ultralight, high-performance electromagnetic interference (EMI) shielding graphene foam (GF)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) composites are developed by drop coating of PEDOT:PSS on cellular-structured, freestanding GFs. To enhance the wettability and the interfacial bonds with PEDOT:PSS, GFs are functionalized with 4-dodecylbenzenesulfonic acid. The GF/PEDOT:PSS composites possess an ultralow density of 18.2 × 10 g/cm and a high porosity of 98.8%, as well as an enhanced electrical conductivity by almost 4 folds from 11.8 to 43.2 S/cm after the incorporation of the conductive PEDOT:PSS. Benefiting from the excellent electrical conductivity, ultralight porous structure, and effective charge delocalization, the composites deliver remarkable EMI shielding performance with a shielding effectiveness (SE) of 91.9 dB and a specific SE (SSE) of 3124 dB·cm/g, both of which are the highest among those reported in the literature for carbon-based polymer composites. The excellent electrical conductivities of composites arising from both the GFs with three-dimensionally interconnected conductive networks and the conductive polymer coating, as well as the left-handed composites with absolute permittivity and/or permeability larger than one give rise to significant microwave attenuation by absorption.

The effects of number of graphene layers (n) and size of multilayer graphene sheets on thermal conductivities (TCs) of their epoxy composites are investigated. Molecular dynamics simulations show that the in-plane TCs of graphene sheets and the TCs across the graphene/epoxy interface simultaneously increase with increasing n. However, such higher TCs of multilayer graphene sheets will not translate into higher TCs of bulk composites unless they have large lateral sizes to maintain their aspect ratios comparable to the monolayer counterparts. The benefits of using large, multilayer graphene sheets are confirmed by experiments, showing that the composites made from graphite nanoplatelets (n > 10) with over 30 μm in diameter deliver a TC of ∼1.5 W m(-1) K(-1) at only 2.8 vol %, consistently higher than those containing monolayer or few-layer graphene at the same graphene loading. Our findings offer a guideline to use cost-effective multilayer graphene as conductive fillers for various thermal management applications.