Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C<sub>60</sub>

Yokoi, Hiroki; Hiroto, Satoru; Sakamaki, Daisuke; Seki, Shu; Shinokubo, Hiroshi

doi:10.1039/c7sc04453d

Cited by 48 publications

(34 citation statements)

References 37 publications

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“…formation of complex [4]⊂[C60/70]. 34,49,54,78,79 Concomitant quenching of the PDI fluorescence emission (up to 29 % 95 ) was also observed with C60 (Figure 3a), indicative of intermolecular charge transfer between proximal donor and acceptor molecules (vide infra). 36,49,77,78,96 ), thereby enabling quantification of fullerene binding in solution (Table 1).…”

Section: Fullerene Recognition Studies Toluene and O-dichlorobenzenementioning

confidence: 97%

“…36,38,101 In agreement with previously reported solution phase fullerene recognition studies, C60 binding is stronger in toluene than o-DCB due to the fact that the latter is a more competitive solvent. 54,102 (Add J. Phys. Chem., 1993, 97, 3379 to this ref) However, on moving to the more polar solvent with C70, an enhanced stabilisation of the stronger charge transfer aromatic stacking interactions appears to compensate for this effect.…”

Section: Fullerene Recognition Studies Toluene and O-dichlorobenzenementioning

confidence: 99%

“…122,125 Indeed, to the best of our knowledge, Green Box is the first rationally designed synthetic receptor capable of recognising and sensing a pristine fullerene via thermally promoted SET from host to guest, with previous systems reporting only evidence of partial charge transfer in the ground state. 33,34,47,49,52,54,[126][127][128] Most importantly, SET occurs under ambient conditions; i.e. at room temperature, in oxygenated solvent and is unaffected by natural light (i.e.…”

Section: Nitrobenzenementioning

confidence: 99%

“…52,53 Hosts containing electron rich, lipophilic cavities are also preferential, on the basis of electronic complementarity towards the electron deficient fullerene guest, enabling interactions to be visualized spectroscopically. [52][53][54] When these criteria are satisfied intermolecular partial charge transfer in the ground state and/or full single electron transfer (SET) in the excited state can occur between donor and acceptor. 34,36,42,44 However, thermally promoted SET in the ground state, an extreme of the charge transfer energy continuum, [55][56][57] is, to the best of our knowledge, unprecedented in a rationally designed fullerene-based dyad system.…”

Section: Introductionmentioning

confidence: 99%

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The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes

et al. 2019

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The powerful electron accepting ability of fullerenes makes them ubiquitous components in biomimetic donor-acceptor systems that model the intermolecular electron transfer processes of Nature's photosynthetic centre. Exploiting perylene diimides (PDIs) as components in cyclic host systems for the noncovalent recognition of fullerenes is unprecedented, in part because archetypal PDIs are also electron deficient, making dyad assembly formation electronically unfavourable. To address this, we report the strategic design and synthesis of a novel large, macrocyclic receptor comprised of two covalently strapped electron-rich bis-pyrrolidine PDI panels, nicknamed the "Green Box" due to its colour. Through the principle of electronic complementarity, the Green Box exhibits strong recognition of pristine fullerenes (C60/70), with the non-covalent ground and excited state interactions that occur upon fullerene guest encapsulation characterised by a range of techniques including electronic absorption, fluorescence emission, NMR and time-resolved EPR spectroscopies, cyclic voltammetry and mass spectrometry. Whilst relatively low polarity solvents result in partial charge transfer in the host donor-guest acceptor complex, increasing the polarity of the solvent medium facilitates rare, thermally allowed full electron transfer from Green Box to fullerene in the ground state. Both species in the ensuing charge separated radical ion paired complex are spectroscopically characterised, with thermodynamic reversibility and significant kinetic stability also demonstrated. Importantly, the Green Box represents a seminal type of C60/70 host where electron-rich PDI motifs are utilised as recognition motifs for fullerenes, facilitating novel intermolecular, solvent tuneable ground state electronic communication with these guests. The ability to switch between extremes of the charge transfer energy continuum is without precedent in synthetic fullerene-based dyads.

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Section: Fullerene Recognition Studies Toluene and O-dichlorobenzenementioning

confidence: 97%

Section: Fullerene Recognition Studies Toluene and O-dichlorobenzenementioning

confidence: 99%

Section: Nitrobenzenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes

et al. 2019

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“…6). Here, the synthesis starts with the oxidative dimerization of 9-aminophenanthrene 63 to tetrabenzocarbazole 64 [43][44][45][46] (Fig. 7a) 48 .…”

Section: Reactions Involving Metal Catalysismentioning

confidence: 99%

Synthesis of corannulene-based nanographenes

2019

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Corannulene (C 20 H 10) is a polycyclic hydrocarbon in which five six-membered rings surround a central five-membered ring to construct a bowl-like aromatic structure. Here we examine the development of synthetic strategies that allow for the growth of the peripheral aromatic rings as a means to extend the aromatic area of the central corannulene nucleus and provide access to unique nanocarbon molecules. s p 2-hybridised structures of carbon have fascinated the research community for a very long time. In 1985, buckminsterfullerene, otherwise known as C 60 , was discovered (Fig. 1a) 1. In this ball-shaped molecule, the curvature in the structure stems from the presence of fivemembered rings. In 1991, carbon nanotubes arrived on the scene 2. Here, the structure is cylindrical and composed of only rolled-up six-membered rings. In 2004, a sheet-like single layer from graphite-graphene-was isolated 3. All of these materials were shown to have extraordinary electronic and mechanical properties due to their unique curved or planar sp 2-hybridised aromatic structures. Inspired by these discoveries, chemists have been developing strategies to access such aromatic hydrocarbons through rational ('bottom-up') synthetic approaches. Scott's 12-step chemical synthesis of fullerene C 60 from a rationally designed precursor is a testament to the ingenuity and resourcefulness of organic chemists 4. In planar structures, nanographenes (well-defined cutouts of graphene with nano-scale dimensions) can now be prepared on a regular basis with a very diverse portfolio 5. It is expected that combining the planar structure of graphene with the curvature of fullerenes may produce hybrid materials with interesting properties 6-8. To induce non-planarity into nanographenes, a practical approach would be to introduce a fivemembered ring such as in the case of fullerene, C 60. A perfect building block that allows for such a structural arrangement to happen is corannulene (1)-a molecule in which five six-membered rings surround a central five-membered ring to give a bowl-like structure (Fig. 1b) 9-20. Corannulene also offers many beneficial features as a molecular building block. It has high solubility in common organic solvents. It can be derivatized in a well-defined manner. Due to synthetic ease, the derivatives can be prepared on a multigram scale. These attributes are important as they allow for the scalable preparation of carefully designed corannulene-based building blocks and the subsequent synthesis, purification and structural analysis of the larger (fused) aromatic systems. Recently, therefore, there has been a surge in employment of corannulene as a core molecule in the synthesis of extended aromatic structures. Our aim in this review article is to discuss

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Supramolecular Engineering of Crystalline Fullerene Micro‐/Nano‐Architectures

Bao

Guo

et al. 2022

Advanced Materials

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Fullerenes are a molecular form of carbon allotrope and bear certain solubility, which allow the supramolecular assembly of fullerene molecules—also together with other complementary compound classes—via solution‐based wet processes. By well‐programmed organizing these building blocks and precisely modulating over the assembly process, supramolecularly assembled fullerene micro‐/nano‐architectures (FMNAs) are obtained. These FMNAs exhibit remarkably enhanced functions as well as tunable morphologies and dimensions at different size scales, leading to their applications in diverse fields. In this review, both traditional and newly developed assembly strategies are reviewed, with an emphasis on the morphological evolution mechanism of FMNAs. The discussion is then focused on how to precisely regulate the dimensions and morphologies to generate functional FMNAs through solvent engineering, co‐crystallization, surfactant incorporation, or post‐fabrication treatment. In addition to C60‐based FMNAs, this review particularly focuses on recently fabricated FMNAs comprising higher fullerenes (e.g., C70) and metallofullerenes. Meanwhile, an overview of the property modulation is presented and multidisciplinary applications of FMNAs in various fields are summarized, including sensors, optoelectronics, biomedicines, and energy. At the end, the prospects for future research, application opportunities, and challenges associated with FMNAs are proposed.

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Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C₆₀

Abstract: A directly connected azabuckybowl dimer forms a 1 : 1 complex with C60 in a diluted solution, while 1D chain supramolecular assemblies are obtained upon increasing the concentration.

Cited by 48 publications

References 37 publications

The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes

The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes

Synthesis of corannulene-based nanographenes

Supramolecular Engineering of Crystalline Fullerene Micro‐/Nano‐Architectures

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Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C60

Abstract: A directly connected azabuckybowl dimer forms a 1 : 1 complex with C60 in a diluted solution, while 1D chain supramolecular assemblies are obtained upon increasing the concentration.

Cited by 48 publications

References 37 publications

The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes

The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes

Synthesis of corannulene-based nanographenes

Supramolecular Engineering of Crystalline Fullerene Micro‐/Nano‐Architectures

Contact Info

Product

Resources

About

Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C₆₀