Synthesis and Self‐Assembly of Cyclic 2,7‐Anthrylene Ethynylene 1,3‐Phenylene Ethynylene Trimer with a Planar Conformation

Takaki, Yuta; Ozawa, Ryota; Kajitani, Takashi; Fukushima, Takanori; Mitsui, Masaaki; Kobayashi, Kenji

doi:10.1002/chem.201603627

Cited by 13 publications

(18 citation statements)

References 44 publications

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“…There are recent examples of macrocycles with heteroaromatic building blocks synthesized by Sonogashira coupling. Gong et al reported hexakis( m ‐phenyleneethynylene) macrocycles with multiple H‐bonding side chains and modified cavities forming a helical tubular assembly, whereas Kobayashi et al reported shape‐persistent macrocycles incorporating a cyclic 2,7‐anthryleneethynylene 1,3‐phenyleneethynylene trimer to display self‐organization on surfaces . In the field of molecular electronics, we reported macrocyclic turnstiles comprising a terminally sulfur‐functionalized molecular rod and a redox‐active subunit, to study the switching behavior induced by molecular rotation , …”

Section: Resultsmentioning

confidence: 97%

A Molecular Turnstile as an E‐Field‐Triggered Single‐Molecule Switch: Concept and Synthesis

et al. 2017

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A new single‐molecule switching concept relying on the E‐field‐dependent orientation of a push‐pull system (via its dipole moment) is presented. As first steps towards realizing the E‐field‐triggered single‐molecule motion, the synthesis of turnstile 1, which is designed to bridge a gap within a carbon nanotube junction, is reported. Turnstile 1 consists of a hexakis(m‐phenyleneethynylene) macrocycle decorated with phenanthrene‐functionalized oligo(phenyleneethynylene) (OPE) wires at opposite ends, as well as a para‐connected push‐pull rod as rotator unit. The similarity of the rotor dimension with the surrounding macrocycle guarantees efficient π‐stacking between both subunits when an E‐field is applied. To introduce a dipole moment into the rotator, the structure is terminally functionalized with a nitrile group on one side and with a dimethylamino group on the opposite end. Synthetic protocols based on Sonogashira–Hagihara couplings were developed to build up the macrocycle scaffold. The highly functionalized open precursor A is the key building block of the sequence as it allows a twofold intramolecular palladium‐catalyzed cyclization reaction to be performed to obtain the target turnstile in a very good yield of 68 %. The target structure was fully characterized by NMR spectroscopy and mass spectrometry. Furthermore, 1H‐1H NOESY NMR experiments pointed to a pseudo‐rotation of the push‐pull rod within the turnstile structure on the time scale of the NMR experiment.

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Section: Resultsmentioning

confidence: 97%

A Molecular Turnstile as an E‐Field‐Triggered Single‐Molecule Switch: Concept and Synthesis

et al. 2017

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“…It is well known that π‐stacking causes the upfield shifting of the NMR signals due to the mutual shielding of the aromatic rings . Accordingly, a concentration‐dependent 1 H‐NMR study in chloroform was carried out as a first step to explore this possibility.…”

Section: Resultsmentioning

confidence: 99%

Self‐Assembly of Clicked Star‐Shaped Triazines into Functional Nanostructures

et al. 2018

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Two non-amphiphilic star-shaped 2,4,6-tris(1,2,3triazol-4-yl)-1,3,5-triazines showing different behavior in terms of self-assembly and luminescent properties are described. They aggregate in the liquid phase to form low-dimensional nanostructures with a variety of morphologies, such as spherical particles, one-hole hollow spheres, toroids, twisted fibers or helical nanotubes, just by varying the conditions of a straightforward reprecipitation method. Aggregation has an opposite effect concerning the fluorescent properties of the proposed compounds, either causing the enhancement or the quenching of the emission after the self-assembly. Quantum chemical calculations have been also performed to assist in the structural and electronic characterization of the two star-shaped compounds.

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“…The 1 HNMR chemical shifts of non-exchangeable aromatic protons for a,w-2OD-TIFDMT were highly dependent on the concentration. [31] This is probably ar esult of highly favorable inter-molecular interactions, such as donor-acceptor,d ipole-dipole, and p-p stacking between D-A-D p cores. This indicates the presence of strong selfassociation between a,w-2OD-TIFDMT molecules in the solution phase.…”

Section: Synthesis and Structural/thermal Characterizationsmentioning

confidence: 99%

“…3.6!14.4 mm), the self-association between a,w-2OD-TIFDMT molecules is expected to be as stronga st hat measured for previously reported macrocyclic p-conjugated systems, if not stronger. [31] This is probably ar esult of highly favorable inter-molecular interactions, such as donor-acceptor,d ipole-dipole, and p-p stacking between D-A-D p cores.…”

Section: Synthesis and Structural/thermal Characterizationsmentioning

confidence: 99%

A Solution‐Processable Liquid‐Crystalline Semiconductor for Low‐Temperature‐Annealed Air‐Stable N‐Channel Field‐Effect Transistors

et al. 2017

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A new solution-processable and air-stable liquid-crystalline n-channel organic semiconductor (2,2'-(2,8-bis(5-(2-octyldodecyl)thiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile, α,ω-2OD-TIFDMT) with donor-acceptor-donor (D-A-D) π conjugation has been designed, synthesized, and fully characterized. The new semiconductor exhibits a low LUMO energy (-4.19 eV) and a narrow optical bandgap (1.35 eV). The typical pseudo-focal-conic fan-shaped texture of a hexagonal columnar liquid-crystalline (LC) phase was observed over a wide temperature range. The spin-coated semiconductor thin films show the formation of large (≈0.5-1 μm) and highly crystalline platelike grains with edge-on molecular orientations. Low-temperature-annealed (50 °C) top-contact/bottom-gate OFETs have provided good electron mobility values as high as 0.11 cm (V s) and high I /I ratios of 10 to 10 with excellent ambient stability. This indicates an enhancement of two orders of magnitude (100×) when compared with the β-substituted parent semiconductor, β-DD-TIFDMT (2,2'-(2,8-bis(3-dodecylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile). The current rational alkyl-chain engineering route offers great advantages for D-A-D π-core coplanarity in addition to maintaining good solubility in organic solvents, and leads to favorable optoelectronic/physicochemical characteristics. These remarkable findings demonstrate that α,ω-2OD-TIFDMT is a promising semiconductor material for the development of n-channel OFETs on flexible plastic substrates and LC-state annealing of the columnar liquid crystals can lower the electron mobility for transistor-type charge transport.

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Synthesis and Self‐Assembly of Cyclic 2,7‐Anthrylene Ethynylene 1,3‐Phenylene Ethynylene Trimer with a Planar Conformation

Cited by 13 publications

References 44 publications

A Molecular Turnstile as an E‐Field‐Triggered Single‐Molecule Switch: Concept and Synthesis

A Molecular Turnstile as an E‐Field‐Triggered Single‐Molecule Switch: Concept and Synthesis

Self‐Assembly of Clicked Star‐Shaped Triazines into Functional Nanostructures

A Solution‐Processable Liquid‐Crystalline Semiconductor for Low‐Temperature‐Annealed Air‐Stable N‐Channel Field‐Effect Transistors

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