Visualizing the helical stacking of octahedral metallomesogens with a chiral core

Watanabe, Go; Watanabe, Hironori; Suzuki, Kota; Yuge, Hidetaka; Yoshida, Shintaro; Mandai, Takuyoshi; Yoneda, Shigetaka; Sato, Hisako; Hara, Mitsuo; Yoshida, Jun

doi:10.1039/d0cc05930g

Cited by 7 publications

(8 citation statements)

References 37 publications

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“…The construction of molecular force fields also remains challenging for room-temperature ionic liquids because of the many-body effects of polarization and charge transfer in condensed phase (42)(43)(44)(45)(46)(47)(48)(49). Although MD simulations enable to observe structural ordering of nonionic LC molecules and self-assembled nanostructures of amphiphilic compounds (39,(50)(51)(52)(53)(54)(55), the addition of ionic moieties requires further large system and long relaxation time for an MD simulation (39)(40)(41). These issues may be more amplified in thermotropic ILC compounds.…”

Section: Introductionmentioning

confidence: 99%

Molecular insights on confined water in the nanochannels of self-assembled ionic liquid crystal

et al. 2021

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Self-assembled ionic liquid crystals can transport water and ions via the periodic nanochannels, and these materials are promising candidates as water treatment membranes. Molecular insights on the water transport process are, however, less investigated because of computational difficulties of ionic soft matters and the self-assembly. Here we report specific behavior of water molecules in the nanochannels by using the self-consistent modeling combining density functional theory and molecular dynamics and the large-scale molecular dynamics calculation. The simulations clearly provide the one-dimensional (1D) and 3D-interconnected nanochannels of self-assembled columnar and bicontinuous structures, respectively, with the precise mesoscale order observed by x-ray diffraction measurement. Water molecules are then confined inside the nanochannels with the formation of hydrogen bonding network. The quantitative analyses of free energetics and anisotropic diffusivity reveal that, the mesoscale geometry of 1D nanodomain profits the nature of water transport via advantages of dissolution and diffusion mechanisms inside the ionic nanochannels.

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Section: Introductionmentioning

confidence: 99%

Molecular insights on confined water in the nanochannels of self-assembled ionic liquid crystal

et al. 2021

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“…Compounds 61 and 62 shown in Chart exhibit the typical fan-shaped and focal-conic textures of the SmA mesophase. Although several octahedral metallomesogens were reported by Giroud-Godquin and Rassat, Swager, , Bruce, − Ghedini, and more recently by Watanabe, these species constitute one of the few octahedral Zn(II) species that show mesomorphism . The liquid crystal behavior of these zinc derivatives depend notably on the chain length, the molecular geometry and the nature of the counteranions used.…”

Section: Molecular Architectures Based On Zn(ii) Complexesmentioning

confidence: 97%

Advanced Functional Luminescent Metallomesogens: The Key Role of the Metal Center

2021

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The use of liquid crystals for the fabrication of displays incorporated in technological devices (TVs, calculators, screens of eBook’s, tablets, watches) demonstrates the relevance that these materials have had in our way of living. However, society evolves, and improved devices are looked for as we create a more efficient and safe technology. In this context, metallomesogens can behave as multifunctional materials because they can combine the fluidic state of the mesophases with properties such as photo and electroluminescence, which offers new exciting possibilities in the field of optoelectronics, energy, environment, and even biomedicine. Herein, it has been established the role of the molecular geometry induced by the metal center in metallomesogens to achieve the self-assembly required in the liquid-crystalline mesophase. Likewise, the effect of the coordination environment in metallomesogens has been further analyzed because of its importance to induce mesomorphism. The structural analysis has been combined with an in-depth discussion of the properties of these materials, including their current and potential future applications. This review will provide a solid background to stimulate the development of novel and attractive metallomesogens that allow designing improved optoelectronic and microelectronic components. Additionally, nanoscience and nanotechnology could be used as a tool to approach the design of nanosystems based on luminescent metallomesogens for use in bioimaging or drug delivery.

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“…By increasing the size of the encapsulated metal ion from Li + to Cs + in the C 4 -symmetric tetrameric clusters, the four tail rim regions (defined by cross cone angles and inter-rim distances) of the clusters (i.e., the four p-heptoxyphenyl groups) get closer and closer, thus inducing less and less overall helical twisting strength (i.e., turbo effects) to the nematic E7 LC hosts (Figure 12). 33 Notably, the unprecedented, linear correlations are remarkable in view of the cluster concentration at 0.11 mol %/μm, which amounts to ∼10 ng of encapsulated K + in 3-K in 40 μL of E7 mixture! Scheme 3.…”

Section: ■ Introduction and Backgroundmentioning

confidence: 99%

Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Chen

Weng

2022

Inorg. Chem.

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Vanadyl(V) complexes 1 and 2 bearing a nematic liquid crystal (LC) like a p-heptoxyphenyl group or a fluorous-tag pnonafluoroheptoxyphenyl (NFH) group at the C5 position of the Nsalicylidene template were designed and synthesized. Each complex was subjected to MVO 3 -induced self-assembly to form metal-ion, encapsulated quartet clusters 3-M and 3′-M. The Na + in cluster complex 3-Na or 3′-Na can be readily replaced by Rb + , Ag + , or Hg 2+ in an aqueous layer to form cluster complexes by ion swapping at the H 2 O/CDCl 3 bilayer interface. Selectivity profiles were examined with alkali-metal ions, Ag + , and Hg 2+ through metal-ion competition experiments. The 3′-Na has an exclusive selectivity for Hg 2+ in the presence of Zn 2+ and Cd 2+ . Cluster complexes 3-M were utilized as chiral dopants to nematic LC materials. The effects of the encapsulated metal ions within the alkali family and Ag + on Cano's line widths and helical pitch changes were viewed in wedge cells under a polarized microscope. Their correlations with the ionic radius were identified. The subnano information of the metal ions can thus be asymmetrically amplified to Cano's line spacings of the submilimeter domain. Conversely, the effects of the encapsulated alkali metal ions and Hg 2+ in 3′-M on the interactions of their NFH tails toward fluorous silica gel (FSG) were performed via HPLC analyses. Their retention times became longer as the sizes of encapsulated, alkali metal ions increased. The increasing ion size from Na + to Cs + caused the four lower rim NFH tags of the cluster to be closer due to reduced cone angles. Their interactions among NFH tail groups on FSG became larger, thus leading to distinctive separations with t R from 7.36 to 10.27 min. The retention time difference between 3′-Na and 3′-Hg on HPLC was ∼3.6 min, resulting in discernible separation. The individual ion size differences on the subnano scale can thus be amplified and unambiguously established in the real time domain.

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Visualizing the helical stacking of octahedral metallomesogens with a chiral core

Abstract: The detailed stacking structure of a helical columnar liquid crystal formed by enantiopure octahedral metallomesogens was investigated using both GI-XRD and MD simulation.

Cited by 7 publications

References 37 publications

Molecular insights on confined water in the nanochannels of self-assembled ionic liquid crystal

Molecular insights on confined water in the nanochannels of self-assembled ionic liquid crystal

Advanced Functional Luminescent Metallomesogens: The Key Role of the Metal Center

Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

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