Supramolecular Receptor Design: Anion‐Triggered Binding of C<sub>60</sub>

Nielsen, Kent A.; Cho, Won‐Seob; Sarova, Ginka H.; Petersen, Bo Møller; Bond, Andrew D.; Becher, Jan; Jensen, Frank; Guldi, Dirk M.; Sessler, Jonathan L.; Jeppesen, Jan O.

doi:10.1002/ange.200602724

Cited by 31 publications

(9 citation statements)

References 52 publications

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“…When the compound is treated with chloride anion in solution, it produces a bowl-like receptor that is able to encapsulate C 60 in a 2 : 1 barrel-like manner. The green color of the complex 22ÁCl À1 ÁC 60 clearly indicates favorable CT interactions between the TTF donor units and the C 60 moiety [41]. Lee and coworkers also reported that calix [1]pyreno [3]pyrrole 23 exhibits considerably high binding affinity for C 70 Fukazawa and Haino found that calix [5]arene 3b forms a 1 : 1 complex in solution, but it does form a 1 : 2 complex in the solid state [43].…”

Section: Modified Traditional Host Moleculesmentioning

confidence: 99%

Receptors for Pristine Fullerenes Based on Concave–Convex π–πInteractions

Kawase

2012

Supramolecular Chemistry of Fullerenes and Carbon Nanotubes

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In 1990, Kr€ atchmer and coworkers reported the extraction of fullerenes (C 60 and C 70 ) from carbon soot using aromatic solvents (Figure 3.1) [1]. After this discovery, receptor molecules for fullerenes have been extensively studied for separation and purification of fullerenes. Supramlecular chemists have found that traditional host molecules composed of electron-rich aromatic rings such as calix[n]arenes 1-4, oxacalix[3]arenes 5, and cyclotriveratrylenes (CTV) 6 ( Figure 3.2) can be employed for the purpose. The crystallographic analyses of these complexes with C 60 clearly indicated the importance of the p-p interactions between the convex p surface of C 60 and the concave p surface of the traditional host molecules. On the other hand, except a few examples, the traditional hosts bound fullerenes only in solid state. In order to bind with fullerenes more tightly, two strategies have been presented to construct the well preorganized p cavity so far. First, electron-rich aromatic units are introduced to the host molecule as appendants (Figure 3.2a). Second, two host molecules are linked by appropriate tether(s) to form a dimeric structure with a creft-, ring-, or ball-shaped cavity (Figure 3.2b). The binding abilities of the modified receptors fairly increased in comparison with those of simple traditional hosts. On the other hand, new receptors based on curved conjugated systems such as corannulene 7, extended TTF (exTTF) 8, and carbon nanorings (Figure 3.3) have been developed recently. These compounds possess a concave p surface matching to the convex surface of C 60 . Cyclic [6]paraphenyleneacetylene ([6]CPPA) 9 and the related compounds have smooth belt-shaped structure similar to a cut piece of carbon nanotube, and thus may be termed carbon nanorings. These receptors form stable inclusion complexes with fullerenes both in solution and in the solid state, and are good model compounds to explore the nature of the concave-convex p-p interactions. This chapter discusses the fullerene receptors bearing a cavity surrounded by p-orbitals, the so-called p cavity, the concept of molecular designs, and the nature of p-p interactions. The survey of the fullerene receptors should provide an insight into the supramolecular properties of curved conjugated systems. Although the receptor Supramolecular Chemistry of Fullerenes and Carbon Nanotubes, First Edition. Edited by Nazario Martin and Jean-Francois Nierengarten.

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Section: Modified Traditional Host Moleculesmentioning

confidence: 99%

Receptors for Pristine Fullerenes Based on Concave–Convex π–πInteractions

Kawase

2012

Supramolecular Chemistry of Fullerenes and Carbon Nanotubes

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“…Scheme 84) shows much higher affinity towards neutral guests like imidazolidin-2-one after binding of trifluoroacetate. [143] They found that calixpyrrole 104 forms a bowl-shaped structure when a chloride ion is bound via four hydrogen-bonds in the center of the molecule. [143] They found that calixpyrrole 104 forms a bowl-shaped structure when a chloride ion is bound via four hydrogen-bonds in the center of the molecule.…”

Section: Heterotropic Systemsmentioning

confidence: 99%

“…[142] An allosteric receptor for the recognition of C 60 consisting of two subunits has been put forward by Sessler and Jeppe- www.chemeurj.org sen and co-workers. [143] They found that calixpyrrole 104 forms a bowl-shaped structure when a chloride ion is bound via four hydrogen-bonds in the center of the molecule. Two of these bowls then have an optimal size to encapsulate C 60 (Scheme 69).…”

Section: Heterotropic Systemsmentioning

confidence: 99%

Artificial Allosteric Receptors

Kremer¹,

Lützen²

2013

Chemistry A European J

133

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Cooperative effects in the binding of two or more substrates to different binding sites of a receptor that are a result of a conformational change caused by the binding of the first substrate--also referred to as the effector--are called allosteric effects. In biological systems, allosteric regulation is a widely used mechanism to control the function of proteins and enzymes in cellular metabolism. Inspired by this a lot of efforts have been made in supramolecular chemistry to implement this concept into artificial systems to control functions as molecular recognition, signal amplification, or even reactivity and catalysis. This review gives an up-to-date overview over the different approaches that have been reported ever since the first examples from the late 1970s/early 1980s. It covers both homo- and heterotropic examples and is divided according to the nature of the effector--cationic, anionic, or neutral--effectors and systems that use combinations of those.

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“…In previous work, we found that these macrocycles would bind planar, electron-deficient nitroaromatics, including TNB, with a 1∶2 stoichiometry in their 1,3-alternate forms in the absence of anions (24,25). In contrast, the corresponding anion-stabilized cone forms would interact with larger electron-deficient species, as evidenced by the anion-triggered binding of C 60 (26) or the stabilization of a long-lived electron transfer state as the result of supramolecular capsule formation (27). The fact that we could stabilize such discrete supramolecular structures led us to consider that doubly functionalized electron-deficient guest species, such as 4 and 5, could be utilized as ditopic macrocyclic building blocks to create self-assembled polymeric arrays.…”

mentioning

confidence: 93%

Chemoresponsive alternating supramolecular copolymers created from heterocomplementary calix[4]pyrroles

Park

Yoon

Kim

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

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The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix [4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix [4] pyrrole. The resulting polymeric materials, stabilized by combination of donor-acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1-and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of "smart" sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling.cooperativity | sensing | supramolecular chemistry | supramolecular polymers | dynamic materials I n recent years, considerable effort has been devoted to the development of artificial supramolecular polymeric materials (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20). Much of the interest in these kinds of systems stems from an appreciation that they act as rudimentary models for some of the most fundamental, yet complex systems, found in nature. Living systems typically exploit multiple noncovalent interactions to drive the formation and stabilization of a wide variety of complex polymeric architectures for the implementation of function, codifying diversity, and imparting complexity. Because of their stabilization, in part by multiple weak forces, including hydrogen bonds, metal-ligand interactions, and donor-acceptor interactions, many of these architectures undergo considerable modification in their structure and function upon application of some external stress or exposure to a specific chemical trigger, as ill...

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Supramolecular Receptor Design: Anion‐Triggered Binding of C₆₀

Cited by 31 publications

References 52 publications

Receptors for Pristine Fullerenes Based on Concave–Convex π–πInteractions

Receptors for Pristine Fullerenes Based on Concave–Convex π–πInteractions

Artificial Allosteric Receptors

Chemoresponsive alternating supramolecular copolymers created from heterocomplementary calix[4]pyrroles

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Supramolecular Receptor Design: Anion‐Triggered Binding of C60

Cited by 31 publications

References 52 publications

Receptors for Pristine Fullerenes Based on Concave–Convex π–πInteractions

Receptors for Pristine Fullerenes Based on Concave–Convex π–πInteractions

Artificial Allosteric Receptors

Chemoresponsive alternating supramolecular copolymers created from heterocomplementary calix[4]pyrroles

Contact Info

Product

Resources

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Supramolecular Receptor Design: Anion‐Triggered Binding of C₆₀