Fullerene receptor based on calix[5]arene through metal-assisted self-assembly

Haino, Takeharu; Araki, Hiromi; Yamanaka, Yuko; Fukazawa, Yoshimasa

doi:10.1016/s0040-4039(01)00420-8

Cited by 59 publications

(28 citation statements)

References 24 publications

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“…Thesynthesis of poly-1 was started from cavitand 4 reported by Sherman et al [18] Thet reatment of 4 with tertbutyldimethylsilylchloride in the presence of N,N-dimethylpyridine gave cavitand 5,which was subjected to n-butyllithium at À78 8 8C, followed by the treatment of iodine to produce the tetraiodo cavitand 6 in good yield. TheS uzuki crosscoupling reaction of 6 with 5-(4-(pinacolatoboryl)phenyl)-2,2'-bipyridine [19] smoothly proceeded to afford the wallextended cavitand 7.T he deprotection of the silyl groups, followed by the condensation with the benzoic acid derivative possessing the reversible addition-fragmentationchain transfer (RAFT) agent to furnish cavitand 3.T he polymerappended cavitand poly-3 was prepared through the RAFT polymerization of cavitand 3 in styrene at 90 8 8C. Thenumberaverage molecular weight of poly-3 was found to be 10 100 gmol À1 with ap olydispersity index (PDI) of 1.18 and ad egree of polymerization (DP) value of 18.…”

Section: Synthesis Of Polymersmentioning

confidence: 99%

Self‐Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand‐Based Coordination Capsules

et al. 2020

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The repeating guest units of poly‐(R)‐2 were selectively encapsulated by the self‐assembled capsule poly‐1 possessing eight polymer side chains to form the supramolecular graft polymer (poly‐1)n⋅poly‐(R)‐2. The encapsulation of the guest units was confirmed by 1H NMR spectroscopy and the DOSY technique. The hydrodynamic radius of the graft polymer structure was greatly increased upon the complexation of poly‐1. The supramolecular graft polymer (poly‐1)n⋅poly‐(R)‐2 was stably formed in the 1:1 host–guest ratio, which increased the glass transition temperature by more than 10 °C compared to that of poly‐1. AFM visualized that (poly‐1)n⋅poly‐(R)‐2 formed the networked structure on mica. The (poly‐1)n⋅poly‐(R)‐2 gelled in 1,1,2,2‐tetrachloroethane, which led to fabrication of distinct viscoelastic materials that demonstrated self‐healing behavior in a tensile test.

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Section: Synthesis Of Polymersmentioning

confidence: 99%

Self‐Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand‐Based Coordination Capsules

et al. 2020

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“…Claessens, and Diederich and Dalcanales groups also described self-assembled cage-shaped molecules based on two subphthalocyanine units 26 [49] and two cavitand units 27 [50], respectively. Calix [5]arene derivatives prepared by Fukazawas group construct the dimeric structure 28 in the presence of silver (I) or copper (II) ions to catch a C 60 molecule in the resulting cavity [51,52]. These cage molecules involving metal cation(s) show relatively small K a values probably due to the high molecular mobility.…”

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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“…In common Ag-bipyridine complexes, the energy barrier for the exchange between the free and the complexed states is small. [20] This high kinetic stability of capsule 1·4 BF 4 would be a result of the cooperative complexation of the bipyridine units.…”

Section: Resultsmentioning

confidence: 99%

Guest Encapsulation and Self‐Assembly of a Cavitand‐Based Coordination Capsule

Haino

Kobayashi

Fukazawa

2006

Chemistry A European J

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The synthesis and spectroscopic characterization of a cavitand-based coordination capsule 14 BF4 of nanometer dimensions is described. Encapsulation studies of large aromatic guests as well as aliphatic guests were performed by using 1H NMR spectroscopy in [D1]chloroform. In addition to the computational analysis of the shape and geometry of the capsule, an experimental approach to estimate the interior size of the cavity is discussed. The cavity provides a highly rigid binding space in which molecules with lengths of approximately 14 A can be selectively accommodated. The rigid cavity distinguished slight structural differences in the flexible alkyl-chain guests as well as the rigid aromatic guests. The detailed thermodynamic studies revealed that not only CH-pi interactions between the methyl groups on the guest termini and the aromatic cavity walls, but also desolvation of the inner cavity play a key role in the guest encapsulation. The cavity preferentially selected the hydrogen-bonded heterodimers of a mixture of two or three carboxylic acids 18-20. The chiral capsule encapsulated a chiral guest to show diastereoselection.

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Fullerene receptor based on calix[5]arene through metal-assisted self-assembly

Cited by 59 publications

References 24 publications

Self‐Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand‐Based Coordination Capsules

Self‐Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand‐Based Coordination Capsules

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

Guest Encapsulation and Self‐Assembly of a Cavitand‐Based Coordination Capsule

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