Selenium and Tellurium Derivatives of Corannulene: Serendipitous Discovery of a One‐Dimensional Stereoregular Coordination Polymer Crystal Based on Te‐O Backbone and Side‐Chain Aromatic Array

Barát, Viktor; Stuparu, Mihaiela C.

doi:10.1002/chem.202003989

Cited by 8 publications

(8 citation statements)

References 75 publications

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“…Another milestone was reported in 2012, featuring pentakis(pinacolatoboryl)corannulene 2 [7h] by regioselective iridium‐catalyzed borylation reaction. Various kinds of sym ‐penta‐substituted corannulene derivatives can be prepared from these materials, [7] including pentaaryl‐, [7b,i] pentaalkynyl‐, [7b,d,e] pentaoxy‐, [7b] pentafluoro‐, [7l] pentathio‐, [7a–c,j,k,n] pentaselenyl‐corannulenes [7m,n] . Yet, other kinds of quintuply substituted corannulenes such as pentaphosphinyl‐, pentaphosphoryl‐, and pentaamino‐corannulenes have not been explored.…”

Section: Methodsmentioning

confidence: 99%

Five‐fold‐symmetric Pentabromo‐ and Pentaiodo‐corannulenes: Useful Precursors of Heteroatom‐substituted Corannulenes

et al. 2021

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Five‐fold‐symmetric pentabromo‐ and pentaiodo‐corannulenes were synthesized in sub‐gram scale in high yields under aerial conditions and were purified without any chromatographic separations. The obtained pentahalocorannulenes were fully characterized by NMR, MS, and X‐ray crystallography. The pentahalocorannulenes are useful precursors of five‐fold symmetric heteroatom‐substituted corannulenes that are difficult‐to‐address from known corannulene derivatives. As a representative example, pentaphosphinylated corannulene was prepared for the first time and was comprehensively characterized.

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Section: Methodsmentioning

confidence: 99%

Five‐fold‐symmetric Pentabromo‐ and Pentaiodo‐corannulenes: Useful Precursors of Heteroatom‐substituted Corannulenes

et al. 2021

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“…Encouraged by these studies, we planned the synthesis of selenoether analogues and their oxidation to selenones (36− 40) in an effort to further enhance the electron affinity of the corannulene nucleus (Figure 10). 41 We observed that while the synthesis of some of the selenoethers are feasible, these compounds become unstable once they are oxidized. Therefore, they are of little value as electron acceptors.…”

Section: Non-fullerene Electron Acceptorsmentioning

confidence: 99%

“…Our interest in corannulene chalcogenides (see Section 2.2.) motivated us to synthesize a tellurium derivative 41 which was observed to oxidize to 9 during either the reaction or the purification process (Scheme 5). An examination with X-ray crystallography revealed that the oxide 9 gave rise to linear polymer chains (10) in the solid state.…”

Section: Scheme 2 Different Synthetic Approaches To Access Corannulen...mentioning

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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“…Tellurium is the heaviest, non-radioactive member of the chalcogen family after oxygen, sulfur, and selenium. 127–131 The unique properties of tellurium compounds are becoming increasingly crucial in inorganic and organic chemistry and materials science. The use of tellurium to replace selenium or sulfur in conjugated polymers provides these materials with new properties, including high polarization and dielectric constant, red-shifted optical absorption, and strong intermolecular interactions.…”

Section: Four Branches Of Polymer Crystalsmentioning

confidence: 99%

“…Then, a similar work on a 1D coordination polymer crystal based on a Te–O backbone was published by Barat et al in 2020. 128 The tellurium derivative was still monomeric in solution, and the crystal corannulene side chains that produced linear polymer chains formed a line spontaneously. Similarly, the polymer backbone was also made of tellurium–oxygen bonds (Fig.…”

Section: Four Branches Of Polymer Crystalsmentioning

confidence: 99%

Recent progress in single-crystal structures of organic polymers

et al. 2022

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Selenium and Tellurium Derivatives of Corannulene: Serendipitous Discovery of a One‐Dimensional Stereoregular Coordination Polymer Crystal Based on Te‐O Backbone and Side‐Chain Aromatic Array

Abstract: Chemistry-A European Journal Scheme1.Synthesis of selenium derivatives of corannulene. Scheme2.Synthesis of at ellurium derivative of corannulene.

Cited by 8 publications

References 75 publications

Five‐fold‐symmetric Pentabromo‐ and Pentaiodo‐corannulenes: Useful Precursors of Heteroatom‐substituted Corannulenes

Five‐fold‐symmetric Pentabromo‐ and Pentaiodo‐corannulenes: Useful Precursors of Heteroatom‐substituted Corannulenes

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

Recent progress in single-crystal structures of organic polymers

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