Cyclic Host Liquids for Facile and High-Yield Synthesis of [2]Rotaxanes

Ogoshi, Tomoki; Aoki, Tatsuto; Shiga, Ryohei; Iizuka, Ryo; Ueda, Seita; Demachi, Kazuki; Yamafuji, Daiki; Kayama, Hitoshi; Yamagishi, Toshio

doi:10.1021/ja310757p

Cited by 100 publications

(63 citation statements)

References 50 publications

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“…97,240 These systems existed in the liquid state over a wide range of temperatures and were stable up to 250°C. These systems could therefore be used as solvents for host−guest complexation processes and the formation of rotaxanes.…”

Section: Bulk Supramolecular Assemblies Constructed From Pillar[n]arenesmentioning

confidence: 99%

Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry

2016

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In 2008, we reported a new class of pillar-shaped macrocyclic hosts, known as "pillar[n]arenes". Today, pillar[n]arenes are recognized as key players in supramolecular chemistry because of their facile synthesis, unique pillar shape, versatile functionality, interesting host-guest properties, and original supramolecular assembly characteristics, which have resulted in numerous electrochemical and biomedical material applications. In this Review, we have provided historical background to macrocyclic chemistry, followed by a detailed discussion of the fundamental properties of pillar[n]arenes, including their synthesis, structure, and host-guest properties. Furthermore, we have discussed the applications of pillar[n]arenes to materials science, as well as their applications in supramolecular chemistry, in terms of their fundamental properties. Finally, we have described the future perspectives of pillar[n]arene chemistry. We hope that this Review will provide a useful reference for researchers working in the field and inspire discoveries concerning pillar[n]arene chemistry.

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Section: Bulk Supramolecular Assemblies Constructed From Pillar[n]arenesmentioning

confidence: 99%

Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry

2016

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“…Recently, solvent-free, nonvolatile, room-temperature functional molecular liquids (FMLs) 7 have emerged as a new generation of liquid materials. With an excellent processability, free deformability, and high thermal stability, FMLs have gained extensive interest in wide areas, including luminescence 8–14 , photoconduction 15–18 , molecular recognition 19, 20 , energy storage 21, 22 , and biological systems 23, 24 . Aiming for applications in flexible and bendable optoelectronics, we 8–10, 15, 16, 25, 26 and others 11–13, 21, 27–32 have developed the alkyl-π engineering strategy 33 to prepare various alkylated-π FMLs by attaching bulky and flexible alkyl chains to optoelectronically active π-conjugated units.…”

Section: Introductionmentioning

confidence: 99%

A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe

Takaya

Iwata

et al. 2017

Sci Rep

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Solvent-free, nonvolatile, room-temperature alkylated-π functional molecular liquids (FMLs) are rapidly emerging as a new generation of fluid matter. However, precision design to tune their physicochemical properties remains a serious challenge because the properties are governed by subtle π-π interactions among functional π-units, which are very hard to control and characterize. Herein, we address the issue by probing π-π interactions with highly sensitive pyrene-fluorescence. A series of alkylated pyrene FMLs were synthesized. The photophysical properties were artfully engineered with rational modulation of the number, length, and substituent motif of alkyl chains attached to the pyrene unit. The different emission from the excimer to uncommon intermediate to the monomer scaled the pyrene-pyrene interactions in a clear trend, from stronger to weaker to negligible. Synchronously, the physical nature of these FMLs was regulated from inhomogeneous to isotropic. The inhomogeneity, unexplored before, was thoroughly investigated by ultrafast time-resolved spectroscopy techniques. The result provides a clearer image of liquid matter. Our methodology demonstrates a potential to unambiguously determine local molecular organizations of amorphous materials, which cannot be achieved by conventional structural analysis. Therefore this study provides a guide to design alkylated-π FMLs with tailorable physicochemical properties.

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“…Exciting examples are solvent-free liquids that enhance the performance of dyes, 1 create permanent liquid porosity, 2 or increase reaction yields by unprecedentedly high concentrations. 3 …”

Section: Introductionmentioning

confidence: 99%

Liquefaction of Biopolymers: Solvent-free Liquids and Liquid Crystals from Nucleic Acids and Proteins

Liu

Göstl

et al. 2017

Acc. Chem. Res.

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ConspectusBiomacromolecules, such as nucleic acids, proteins, and virus particles, are persistent molecular entities with dimensions that exceed the range of their intermolecular forces hence undergoing degradation by thermally induced bond-scission upon heating. Consequently, for this type of molecule, the absence of a liquid phase can be regarded as a general phenomenon. However, certain advantageous properties usually associated with the liquid state of matter, such as processability, flowability, or molecular mobility, are highly sought-after features for biomacromolecules in a solvent-free environment. Here, we provide an overview over the design principles and synthetic pathways to obtain solvent-free liquids of biomacromolecular architectures approaching the topic from our own perspective of research. We will highlight the milestones in synthesis, including a recently developed general surfactant complexation method applicable to a large variety of biomacromolecules as well as other synthetic principles granting access to electrostatically complexed proteins and DNA.These synthetic pathways retain the function and structure of the biomacromolecules even under extreme, nonphysiological conditions at high temperatures in water-free melts challenging the existing paradigm on the role of hydration in structural biology. Under these conditions, the resulting complexes reveal their true potential for previously unthinkable applications. Moreover, these protocols open a pathway toward the assembly of anisotropic architectures, enabling the formation of solvent-free biomacromolecular thermotropic liquid crystals. These ordered biomaterials exhibit vastly different mechanical properties when compared to the individual building blocks. Beyond the preparative aspects, we will shine light on the unique potential applications and technologies resulting from solvent-free biomacromolecular fluids: From charge transport in dehydrated liquids to DNA electrochromism to biocatalysis in the absence of a protein hydration shell. Moreover, solvent-free biological liquids containing viruses can be used as novel storage and process media serving as a formulation technology for the delivery of highly concentrated bioactive compounds. We are confident that this new class of hybrid biomaterials will fuel further studies and applications of biomacromolecules beyond water and other solvents and in a much broader context than just the traditional physiological conditions.

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Cyclic Host Liquids for Facile and High-Yield Synthesis of [2]Rotaxanes

Cited by 100 publications

References 50 publications

Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry

Pillar-Shaped Macrocyclic Hosts Pillar[n]arenes: New Key Players for Supramolecular Chemistry

A Guide to Design Functional Molecular Liquids with Tailorable Properties using Pyrene-Fluorescence as a Probe

Liquefaction of Biopolymers: Solvent-free Liquids and Liquid Crystals from Nucleic Acids and Proteins

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