Order–Disorder Transition of Dipolar Rotor in a Crystalline Molecular Gyrotop and Its Optical Change

Setaka, Wataru; Yamaguchi, Kentaro

doi:10.1021/ja408405f

Cited by 100 publications

(74 citation statements)

References 45 publications

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“…The concomitant presence of the tight binding and the dynamic supramolecular complex should be of great interest for the theoretical studies, and the helical environment found on the Hirshfeld surface is of special interest for its effect on the dynamic motion. Furthermore, because the peapod bearing of discrete molecules provides access to a homochiral columnar assembly in the crystalline solid state, an interesting possibility of synchronized orientations of single-axis motion of the peapod bearing may be exploited (35,36). The manipulation of the periodicity of C 60 sites in the tubular column through designing the interdigitated chains as a spacer is also of great interest (37).…”

Section: Discussionmentioning

confidence: 99%

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: Discussionmentioning

confidence: 99%

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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“…Such rotation demonstrates promise as a new class of mechanical switches, compasses, and gyroscopes. [189][190][191][192][193] When the rotor units contain an electric dipole, amphidynamic crystals may also provide an avenue for tunable dielectrics. [194][195][196] Solid-state NMR techniques are useful characterization methods to determine molecular order and the gyroscopic dynamics within amphidynamic crystals when rotors contain atoms that occupy multiple magnetically non-equivalent sites.…”

Section: Acs Nanomentioning

confidence: 99%

Controlling Motion at the Nanoscale: Rise of the Molecular Machines

et al. 2015

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As our understanding and control of intra- and intermolecular interactions evolve, ever more complex molecular systems are synthesized and assembled that are capable of performing work or completing sophisticated tasks at the molecular scale. Commonly referred to as molecular machines, these dynamic systems comprise an astonishingly diverse class of motifs and are designed to respond to a plethora of actuation stimuli. In this Review, we outline the conditions that distinguish simple switches and rotors from machines and draw from a variety of fields to highlight some of the most exciting recent examples of opportunities for driven molecular mechanics. Emphasis is placed on the need for controllable and hierarchical assembly of these molecular components to display measurable effects at the micro-, meso-, and macroscales. As in Nature, this strategy will lead to dramatic amplification of the work performed via the collective action of many machines organized in linear chains, on functionalized surfaces, or in three-dimensional assemblies.

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“…[9] Form olecular crystals,t he dielectric transition between low-and high-dielectric states is established by the reorientation transformation of polar components between static (that is,f rozen) and dynamic (motional) phases,w hich are often accompanied by as tructural phase transition (PT). [12][13][14][15][16][17][18][19][20] Among the various stimuli, temperature is the most frequently used trigger.I nc ontrast, fewer results have been reported on responsive materials that are triggered by stimuli besides temperature. [12][13][14][15][16][17][18][19][20] Among the various stimuli, temperature is the most frequently used trigger.I nc ontrast, fewer results have been reported on responsive materials that are triggered by stimuli besides temperature.…”

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confidence: 99%

A Chemically Triggered and Thermally Switched Dielectric Constant Transition in a Metal Cyanide Based Crystal

et al. 2015

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A dielectric constant transition is chemically triggered and thermally switched in (HPy)2[Na(H2O)Co(CN)6] (2, HPy=pyridinium cation) by single-crystal-to-single-crystal transformation and structural phase transition, respectively. Upon dehydration, (HPy)2[Na(H2O)2Co(CN)6] (1) transforms to its semi-hydrated form 2, accompanying a transition from a low-dielectric state to a high-dielectric state, and vice versa. This dielectric switch is also realized by a structural phase transition in 2 that occurs between room- and low-temperature phases, and which corresponds to high- and low-dielectric states, respectively. The switching property is due to the variation in the environment surrounding the HPy cation, that is, the hydrogen-bonding interactions and the crystal packing, which exert predominant influences on the dynamics of the cations that transit between the static and motional states.

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Order–Disorder Transition of Dipolar Rotor in a Crystalline Molecular Gyrotop and Its Optical Change

Cited by 100 publications

References 45 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

Controlling Motion at the Nanoscale: Rise of the Molecular Machines

A Chemically Triggered and Thermally Switched Dielectric Constant Transition in a Metal Cyanide Based Crystal

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