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  • 1
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    Self-assembly of lattices with high structural complexity from a geometrically simple molecule (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-09-21
    Description: Here we report an anomalous porous molecular crystal built of C–H···N-bonded double-layered roof-floor components and wall components of a segregatively interdigitated architecture. This complicated porous structure consists of only one type of fully aromatic multijoint molecule carrying three identical dipyridylphenyl wedges. Despite its high symmetry, this molecule accomplishes difficult tasks by using two of its three wedges for roof-floor formation and using its other wedge for wall formation. Although a C–H···N bond is extremely labile, the porous crystal maintains its porosity until thermal breakdown of the C–H···N bonds at 202°C occurs, affording a nonporous polymorph. Though this nonporous crystal survives even at 325°C, it can retrieve the parent porosity under acetonitrile vapor. These findings show how one can translate simplicity into ultrahigh complexity.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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  • 2
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    Nematic-to-columnar mesophase transition by in situ supramolecular polymerization (2019)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2019
    Description: 〈p〉Disk- and rod-shaped molecules are incompatible in coassembly, as the former tend to stack one-dimensionally whereas the latter tend to align in parallel. Because this type of incompatibility can be more pronounced in condensed phases, different-shaped molecules generally exclude one another. We report that supramolecular polymerization of a disk-shaped chiral monomer in nematic liquid crystals comprising rod-shaped molecules results in order-increasing mesophase transition into a single mesophase with a core-shell columnar geometry. This liquid crystalline material responds quickly to an applied electric field, resulting in unidirectional columnar ordering. Moreover, it can be modularly customized to be optoelectrically responsive simply by using a photoisomerizable rod-shaped module. The modular strategy allows for cooperative integration of different functions into elaborate dynamic architectures.〈/p〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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  • 3
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    Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-01-05
    Description: Expanding the range of healable materials is an important challenge for sustainable societies. Noncrystalline, high-molecular-weight polymers generally form mechanically robust materials, which, however, are difficult to repair once they are fractured. This is because their polymer chains are heavily entangled and diffuse too sluggishly to unite fractured surfaces within reasonable time scales. Here we report that low-molecular-weight polymers, when cross-linked by dense hydrogen bonds, yield mechanically robust yet readily repairable materials, despite their extremely slow diffusion dynamics. A key was to use thiourea, which anomalously forms a zigzag hydrogen-bonded array that does not induce unfavorable crystallization. Another key was to incorporate a structural element for activating the exchange of hydrogen-bonded pairs, which enables the fractured portions to rejoin readily upon compression.
    Keywords: Materials Science
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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