Corannulene‐Based Electron Acceptors: Combining Modular and Practical Synthesis with Electron Affinity and Solubility

Barát, Viktor; Budanović, Maja; Tam, Si Man; Huh, June; Webster, Richard D.; Stuparu, Mihaiela C.

doi:10.1002/chem.201905521

Cited by 10 publications

(14 citation statements)

References 42 publications

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“…To further ascertain change in the reduction potential of the synthesized molecules, compound 1 was subjected to a debromination reaction to yield corannulene‐amide [33] . The first reduction potential of corannulene‐amide was measured under identical conditions as 4 and 6 and was found to be −1.51 V. This meant that the bilateral aromatic extension in 4 and 6 resulted in an anodic shift of 0.09 and 0.15 V, respectively.…”

Section: Resultsmentioning

confidence: 99%

Bilateral Aromatic Extension of Corannulene Nucleus

et al. 2022

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Herein we show that a dibromo imide derivative of corannulene could be subjected to a palladium‐catalyzed Heck reaction in order to install aryl vinylene groups in a bilateral fashion on the C5‐symmetric aromatic nucleus. A photochemically‐induced oxidative cyclization then affords π‐extended structures in isolated overall yields of 35–44 %. Due to the aromatic area extension and the presence of electron withdrawing groups, the synthesized molecules exhibit an anodic shift of ≈1 V in their first reduction potential as compared to pristine corannulene. The bilateral growth of the aromatic scaffold, therefore, represents a viable strategy to prepare π‐extended corannulenes with an electron deficient character.

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Section: Resultsmentioning

confidence: 99%

Bilateral Aromatic Extension of Corannulene Nucleus

et al. 2022

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“…However, the solubility of the best candidate ( 34 ) is less than optimal in common organic solvents. Therefore, a second molecular design is explored . In this design, an imide group carrying a long solubilizing alkyl chain is introduced in the molecular structure.…”

Section: Discussionmentioning

confidence: 99%

“…Therefore, a second molecular design is explored. 48 In this design, an imide group carrying a long solubilizing alkyl chain is introduced in the molecular structure. Furthermore, fluorinated thiols are used for the nucleophilic substitution reaction.…”

Section: Non-fullerene Electron Acceptorsmentioning

confidence: 99%

Corannulene: A Curved Polyarene Building Block for the Construction of Functional Materials

Stuparu

2021

Acc. Chem. Res.

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Conspectus This Account describes a body of research in the design and synthesis of molecular materials prepared from corannulene. Corannulene (C20H10) is a molecular bowl of carbon that can be visualized as the hydrogen-terminated cap of buckminsterfullerene. Due to this structural resemblance, it is often referred to as a buckybowl. The bowl can invert, accept electrons, and form host–guest complexes. Due to these characteristics, corannulene presents a useful building block in materials chemistry. In macromolecular science, for example, assembly of amphiphilic copolymers carrying a hydrophobic corannulene block enables micelle formation in water. Such micellar nanostructures can host large amounts of fullerenes (C60 and C70) in their corannulene-rich core through complementarity of the curved π-surfaces. Covalent stabilization of the assembled structures then leads to the formation of robust water-soluble fullerene nanoparticles. Alternatively, use of corannulene in a polymer backbone allows for the preparation of electronic and redox-active materials. Finally, a corannulene core enables polymer chains to respond to solution temperature changes and form macroscopic fibrillar structures. In this way, the corannulene motif brings a variety of properties to the polymeric materials. In the design of non-fullerene electron acceptors, corannulene is emerging as a promising aromatic scaffold. In this regard, placement of sulfur atoms along the rim can cause an anodic shift in the molecular reduction potential. Oxidation of the sulfur atoms can further enhance this shift. Thus, a variation in the number, placement, and oxidation state of the sulfur atoms can create electron acceptors of tunable and high strengths. An advantage of this molecular design is that material solubility can also be tuned. For example, water-soluble electron acceptors can be created and are shown to improve the moisture resistance of perovskite solar cells. Host–guest complexation between corannulene and γ-cyclodextrin under flow conditions of a microfluidic chamber allows for the preparation of water-soluble nanoparticles. Due to an oligosaccharide-based sugarcoat, the nanoparticles are biocompatible while the corannulene component renders them active toward nonlinear absorption and emission properties. Together, these attributes allow the nanoparticles to be used as two-photon imaging probes in cancer cells. Finally, aromatic extension of the corannulene nucleus is seen as a potential route to nonplanar nanographenes. Typically, such endeavors rely upon gas-phase synthesis or metal-catalyzed coupling protocols. Recently, two new approaches have been established in this regard. Photochemically induced oxidative cyclization, the Mallory reaction, is shown to be a general method to access corannulenes with an extended π-framework. Alternatively, solid-state ball milling can achieve this goal in a highly efficient manner. These new protocols bring practicality and sustainability to the rapidly growing area of corannulene-based nanographenes. In ...

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“…Having efficient access to thioethers 16 , 19 , and 21 by the aromatic substitution strategy, we began to explore their sulfur oxidation as a means to enhance the electron affinity of the corannulene nucleus (Figure 3). [23,24] The oxidation process could be carried out simply by the addition of meta ‐chloroperbenzoic acid ( m ‐CPBA) at ambient temperature. As an alternative, monoperoxyphthalic acid (MPPA) can also be used.…”

Section: Discussionmentioning

confidence: 99%

“…Overall, three compounds in this series, 20 , 22 , and 29 could reach the first reduction potential of −1 V. However, the best performing molecule, 29 , displayed limited solubility. Therefore, learning from all the experiences thus far in the field, we designed compounds 30 – 33 in which a long alkyl chain afforded solubility in common organic solvents and the combined electron withdrawing power of imide, [28] sulfones, and trifluoromethyl [29,30] groups rendered the aromatic nucleus highly electron deficient ( E red 1 =−1 V) [24] …”

Section: Discussionmentioning

confidence: 99%

Corannulene Chalcogenides

Barát

Stuparu

2020

Chemistry An Asian Journal

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The introduction of chalcogen atoms into a polycyclic aromatic hydrocarbon structure is an established method to tune material properties. In the context of corannulene (C20H10), a fragment of fullerene C60, such structural adjustments have given rise to an emerging class of functional and responsive molecular materials. In this minireview, our aim is to discuss the synthesis and properties of such chalcogen (sulfur, selenium, and tellurium) derivatives of corannulene.

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Corannulene‐Based Electron Acceptors: Combining Modular and Practical Synthesis with Electron Affinity and Solubility

Cited by 10 publications

References 42 publications

Bilateral Aromatic Extension of Corannulene Nucleus

Bilateral Aromatic Extension of Corannulene Nucleus

Corannulene: A Curved Polyarene Building Block for the Construction of Functional Materials

Corannulene Chalcogenides

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