Shape-shifting in contorted dibenzotetrathienocoronenes

Chiu, Chien‐Yang; Kim, Bumjung; Gorodetsky, Alon A.; Sattler, Wesley; Wei, Sujun; Sattler, Aaron; Steigerwald, Michael L.; Nuckolls, Colin

doi:10.1039/c1sc00156f

Cited by 102 publications

(89 citation statements)

References 34 publications

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“…The third molecular conformation [ Figure 4C, the up−down−down−twist−up−down (U−D−D−T−U−D) arrangement] is predicted to be ∼4 kcal/mol higher in energy and has not been observed experimentally. 10 We observe the up−down and butterfly conformations in crystal structures of derivatives of the c-DBTTCs. When the c-DBTTC molecule is substituted with alkyl chains, its crystal structure simultaneously exhibits both the up−down and butterfly conformations.…”

Section: Contorted Hexabenzocoronenementioning

confidence: 95%

Contorted Polycyclic Aromatics

et al. 2014

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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...

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Section: Contorted Hexabenzocoronenementioning

confidence: 95%

Contorted Polycyclic Aromatics

et al. 2014

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“…4). By using thienaldehyde instead of benzaldehyde, this synthetic method provided access to symtribenzotetrathieno-coronenes (TBTTC, 10), which had been sought after previous syntheses of dibenzotetrathienocoronene (DBTTC) 89,90 and hexathienocoronene (HTC) 91,92 (see Fig. Subsequently, TBBs 8 were reacted with three equivalents of benzaldehyde building blocks under the presence of FeCl 3 and acetic anhydride as oxidant/ Lewis acid and dehydrating agent, respectively.…”

Section: Synthesis Of Graphene Moleculesmentioning

confidence: 99%

New advances in nanographene chemistry

et al. 2015

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Nanographenes, or extended polycyclic aromatic hydrocarbons, have been attracting renewed and more widespread attention since the first experimental demonstration of graphene in 2004. However, the atomically precise fabrication of nanographenes has thus far been achieved only through synthetic organic chemistry. The precise synthesis of quasi-zero-dimensional nanographenes, i.e. graphene molecules, has witnessed rapid developments over the past few years, and these developments can be summarized in four categories: (1) non-conventional methods, (2) structures incorporating seven- or eight-membered rings, (3) selective heteroatom doping, and (4) direct edge functionalization. On the other hand, one-dimensional extension of the graphene molecules leads to the formation of graphene nanoribbons (GNRs) with high aspect ratios. The synthesis of structurally well-defined GNRs has been achieved by extending nanographene synthesis to longitudinally extended polymeric systems. Access to GNRs thus becomes possible through the solution-mediated or surface-assisted cyclodehydrogenation, or "graphitization," of tailor-made polyphenylene precursors. In this review, we describe recent progress in the "bottom-up" chemical syntheses of structurally well-defined nanographenes, namely graphene molecules and GNRs.

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“…[79] Katz and co-workers reported in 1991 that addition of propylene oxide improved the reaction and limit the formation of by-products by scavenging the HI formed during the reaction. [80] In the past 10 years,the Katz-modified Mallory reaction has been used to prepare aw ide variety of PA Hs,t he most popular examples being coronenes [81][82][83][84][85] and fused perylenediimides (PDIs). [86][87][88][89][90][91][92][93][94][95] Despite the success of this reaction to prepare nanographenes in high yields,t here are rare examples of its use for the synthesis of GNRs.Nuckolls and co-workers were the first to report the use of the Mallory reaction for the synthesis of finite-length GNRs.Starting from monobromo,dibromo and monostannane derivatives (21-23,S cheme 5), the PDI units were linked together through aS tille coupling using an iterative approach and the rigid ribbon structures were formed by aM allory reaction (compounds [24][25][26].…”

Section: Mallory Reactionmentioning

confidence: 99%

Section: Mallory Reactionmentioning

confidence: 99%

Emerging Bottom‐Up Strategies for the Synthesis of Graphene Nanoribbons and Related Structures

et al. 2019

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The solution‐phase synthesis is one of the most promising strategies for the preparation of well‐defined graphene nanoribbons (GNRs) in large scale. To prepare high quality, defect‐free GNRs, cycloaromatization reactions need to be very efficient, proceed without side reaction and mild enough to accommodate the presence of various functional groups. In this Minireview, we present the latest synthetic approaches for the synthesis of GNRs and related structures, including alkyne benzannulation, photochemical cyclodehydrohalogenation, Mallory and Pd‐ and Ni‐catalyzed reactions.

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Shape-shifting in contorted dibenzotetrathienocoronenes

Cited by 102 publications

References 34 publications

Contorted Polycyclic Aromatics

Contorted Polycyclic Aromatics

New advances in nanographene chemistry

Emerging Bottom‐Up Strategies for the Synthesis of Graphene Nanoribbons and Related Structures

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