Asymmetric Autocatalysis Initiated by Finite Single-Wall Carbon Nanotube Molecules with Helical Chirality

Hitosugi, Shunpei; Matsumoto, Arimasa; Kaimori, Yoshiyasu; Iizuka, Ryosuke; Soai, Kenso; Isobe, Hiroyuki

doi:10.1021/ol403384q

Cited by 27 publications

(11 citation statements)

References 42 publications

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“…The shape index mapping with blue and green areas showed the presence of concave and flat surfaces of the tube, respectively, and should represent a generally typical shape character of the inner surface of SWNT. The green lines of flat areas that appeared helically around the belt region are so significant that shows the presence of a chiral surface inside the helical tube (32). The green dots on the d e mapping appeared under most of the sp 2 -carbon atoms of [4]CC and showed the presence of efficient C host -C guest contacts distributed evenly over the tube.…”

Section: Significancementioning

confidence: 98%

Solid-state structures of peapod bearings composed of finite single-wall carbon nanotube and fullerene molecules

Sato

Yamasaki

Isobe

2014

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

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A supramolecular combination of carbon nanotube and fullerene, so-called a peapod, has attracted much interest, not solely because of its physical properties but also for its unique assembled structures of carbonaceous entities. However, the detailed structural information available was not sufficient for in-depth understanding of its structural chemistry or for exploratory research inspired by novel physical phenomena, mainly because of the severely inhomogeneous nature of currently available carbon nanotubes. We herein report solid-state structures of a molecular peapod. This structure, solved with a belt-persistent finite carbon nanotube molecule at the atomic level by synchrotron X-ray diffraction, revealed the presence of a smooth, inflection-free Hirshfeld surface inside the tube, and the smoothness permitted dynamic motion of the C 60 guest molecule even in the solid state. This precise structural information may inspire the molecular design of carbonaceous machines assembled purely through van der Waals contacts between two neutral molecules. molecular bearing | crystal structure | dynamic solid-state structure | host-guest complex A carbonaceous supramolecular system called a peapod, i.e., a host-guest composite of a single-wall carbon nanotube (SWNT) and fullerene, is attracting considerable interest in various fields due to its unique electronic and molecular structures (1). Although interesting physical phenomena of peapods are being discovered, especially in solid-state physics (2-5), little fundamental and in-depth understanding of peapods has been accumulated at the molecular or atomic levels until quite recently. The first reports of structural chemistry related to peapods appeared through the studies of [10]cycloparaphenylene ([10]CPP) (6): Yamago and coworkers (7) first reported a moderate level of association (association constant K a ∼ 10 3 M in o-dichlorobenzene) with C 60 in the solution phase, and solid-state crystal structures were reported with C 60 and C 70 by Jasti and coworkers (8) and Yamago and coworkers (9). Although this moderate level of association in [10]CPP raised a question regarding the stability of peapods in general (5, 10), we recently showed that the association of belt-persistent tubular molecules, [4]cyclo-2,8-chrysenylenes ([4]CC 2,8 ) (11-13), with C 60 was much higher and recorded a 10 6 -and 10 9 -fold higher association constant in the same medium (K a ∼ 10 9 M) and in benzene (K a ∼ 10 12 M), respectively (Fig. 1A) (14, 15). The level of association in this molecular peapod was comparable to the one expected from theoretical studies with infinite SWNT peapods (10) and, to the best of our knowledge, was highest among host-guest complexes in organic media to date. The uniqueness of molecular recognition in the curved π-systems was further accentuated by the fact that this tight association does not hamper dynamic rolling motions of the guest, providing an intriguing possibility as a molecular bearing (16). To deepen the understanding of tightest host-guest complex ...

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Section: Significancementioning

confidence: 98%

Solid-state structures of peapod bearings composed of finite single-wall carbon nanotube and fullerene molecules

Sato

Yamasaki

Isobe

2014

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

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“…These studies have mainly focused on the influence of the nanoring size and of the building units on the structural, electronic and chiral properties. [3][4][5][6][7][8][9][10][11][12][13][14] As recently reviewed by Jasti and coworkers, 15 nanorings can cover a broad range of applications including imaging tools in biology, 16 complexing agent for single-walled carbon nanotubes 17 or fullerenes, [18][19][20] carbon-based porous material, [21][22] solid state emitters, 11,[23][24] or spin crossover compounds. 25 Molecular nanorings are now considered for their potential applications in organic electronics.…”

Section: Introductionmentioning

confidence: 99%

[4]Cyclo-N-alkyl-2,7-carbazoles: Influence of the Alkyl Chain Length on the Structural, Electronic, and Charge Transport Properties

et al. 2021

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Macrocycles possessing radially oriented π−orbitals have experienced a fantastic development. However, their incorporation in organic electronic devices remains very scarce. In this work, we aim at bridging the gap between organic electronics and nanorings by reporting the first detailed structure-properties-device performance relationship study of organic functional materials based on a nanoring system. Three [4]cyclo-N-alkyl-2,7-carbazoles bearing different alkyl chains on their nitrogen atoms have been synthesized and characterized by combined experimental and theoretical approaches. This study includes electrochemical, photophysical, thermal and structural solid-state measurements and charge transport properties investigations. An optimized protocol of the Pt approach has been developed to synthesize the [4]-cyclocarbazoles in high yield (52-64%), of great interest for further development of nanorings especially in materials science. The charge transport properties of [4]-cyclocarbazoles and a model compound, [8]-cycloparaphenylene ([8]CPP), have been studied. Although no field effect (FE) mobility was recorded for benchmark [8]CPP, FE mobility values of ca 10 -5 cm².V -1 .s -1 were recorded for the [4]-cyclocarbazoles. The characteristics (threshold voltage VTH, subthreshold swing SS, trapping energy ∆E) recorded for the three[4]-cyclocarbazoles appear to be modulated by the alkyl chain length borne by the nitrogen atoms. Remarkably, the space-charge-limited current mobilities measured for the [4]-cyclocarbazoles are about 3 orders of magnitude higher than that of [8]CPP (1.37/ 2.78×10 -4 for the [4]-cyclocarbazoles vs 1.21×10 -7 cm².V -1 .s -1 for [8]CPP) highlighting the strong effect of nitrogen bridges on the charge transport properties. The whole study opens the way to the use of nanorings in electronics, which is now the next step of their developments.

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“…The first publication in 2014 saw the helically chiral (12,8)-[4]CC 2,8 described by Isobe find a practical application in asymmetric catalysis. 93 This collaborative work between Isobe and Soai demonstrated the applicability of enantiopure (12,8)-[4]CC 2,8 in an asymmetric autocatalytic process, namely Soai's addition of di-iso-propylzinc to 2-tert-butylethynylpyrimidine-5carbaldehyde 210. 94 As shown in Scheme 48, addition of 4 equivalents of di-iso-propylzinc to 210 in the presence of 25 mol% of (12,8)-[4]CC 2,8 was then followed by a second addition of larger quantities of 210 (16 equiv.)…”

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confidence: 99%

Cycloparaphenylenes and related nanohoops

2015

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The first synthesis of a cyclic oligophenylene possessing a radial π system was reported in 2008. In the short period that has elapsed since, there has been an ever-increasing level of interest in molecules of this type, as evidenced by the volume of publications in this area. This interest has been driven by the highly unusual properties of these molecules in comparison to their linear oligoarene analogues, as well as the diverse array of potential applications for them. Notably, CPPs and related structures were proposed as viable templates for the bottom-up synthesis of single-walled carbon nanotubes (SWCNTs), a proposition which has recently been realised. This review gives a comprehensive and strictly chronological (by date of first online publication) treatment of literature reports from the inception of the field, with emphasis on both synthesis and properties of CPPs and related nanohoops. (The scope of this review is restricted to molecules possessing a radial π system consisting entirely of subunits which are aromatic in isolation, e.g. CPPs, but not cycloparaphenyleneacetylenes or cyclopolyacetylenes).

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Asymmetric Autocatalysis Initiated by Finite Single-Wall Carbon Nanotube Molecules with Helical Chirality

Abstract: An asymmetric autocatalysis reaction was initiated by a finite single-wall carbon nanotube molecule with helical chirality. The asymmetric induction was initiated by the chiral environment arising from the planar chirality of the tubular polyaromatic hydrocarbons.

Cited by 27 publications

References 42 publications

Solid-state structures of peapod bearings composed of finite single-wall carbon nanotube and fullerene molecules

Solid-state structures of peapod bearings composed of finite single-wall carbon nanotube and fullerene molecules

[4]Cyclo-N-alkyl-2,7-carbazoles: Influence of the Alkyl Chain Length on the Structural, Electronic, and Charge Transport Properties

Cycloparaphenylenes and related nanohoops

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