Magnetic Supramolecular Spherical Arrays: Direct Formation of Micellar Cubic Mesophase by Lanthanide Metallomesogens with 7-Coordination Geometry

Nao Komiyama; Takahiro Ohkubo; Yoshiki Maeda; Yuya Saeki; Nobuyuki Ichikuni; Hyuma Masu; Hirofumi Kanoh; Koji Ohara; Ryunosuke Takahashi; Hiroki Wadati; Hideaki Takagi; Yohei Miwa; Shoichi Kutsumizu; Keiki Kishikawa; Michinari Kohri

doi:10.1002/advs.202309226

Magnetic Supramolecular Spherical Arrays: Direct Formation of Micellar Cubic Mesophase by Lanthanide Metallomesogens with 7-Coordination Geometry

Adv Sci (Weinh). 2024 Mar 13:e2309226. doi: 10.1002/advs.202309226. Online ahead of print.

Authors

Nao Komiyama¹, Takahiro Ohkubo¹, Yoshiki Maeda¹, Yuya Saeki¹, Nobuyuki Ichikuni¹, Hyuma Masu^{1

2}, Hirofumi Kanoh³, Koji Ohara^{4

5}, Ryunosuke Takahashi⁶, Hiroki Wadati^{6

7}, Hideaki Takagi⁸, Yohei Miwa⁹, Shoichi Kutsumizu⁹, Keiki Kishikawa¹, Michinari Kohri¹

Affiliations

¹ Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522, Japan.
² Center for Analytical Instrumentation, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522, Japan.
³ Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522, Japan.
⁴ Faculty of Materials for Energy, Shimane University, 1060, Nishi-Kawatsu-cho, Matsue, Shimane, 690-8504, Japan.
⁵ Diffraction and Scattering Division, Japan Synchrotron Radiation Research Institute, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5198, Japan.
⁶ Department of Material Science, Graduate School of Science, University of Hyogo, 3-2-1 Kouto, Kamigori-cho, Ako-gun, Hyogo, 678-1297, Japan.
⁷ Institute of Laser Engineering, Osaka University, 2-6 Yamadaoka, Suita, Osaka, 565-0871, Japan.
⁸ Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki, 305-0801, Japan.
⁹ Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan.

PMID: 38477513
DOI: 10.1002/advs.202309226

Abstract

Here, an unprecedented phenomenon in which 7-coordinate lanthanide metallomesogens, which align via hydrogen bonds mediated by coordinated H₂ O molecules, form micellar cubic mesophases at room temperature, creating body-centered cubic (BCC)-type supramolecular spherical arrays, is reported. The results of experiments and molecular dynamics simulations reveal that spherical assemblies of three complexes surrounded by an amorphous alkyl domain spontaneously align in an energetically stable orientation to form the BCC structure. This phenomenon differs greatly from the conventional self-assembling behavior of 6-coordinated metallomesogens, which form columnar assemblies due to strong intermolecular interactions. Since the magnetic and luminescent properties of different lanthanides vary, adding arbitrary functions to spherical arrays is possible by selecting suitable lanthanides to be used. The method developed in this study using 7-coordinate lanthanide metallomesogens as building blocks is expected to lead to the rational development of micellar cubic mesophases.

Keywords: 7-coordinate complex; holmium; metallomesogen; micellar cubic mesophase; spherical assembly.

Abstract

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