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

Author:

Komiyama Nao1,Ohkubo Takahiro1ORCID,Maeda Yoshiki1,Saeki Yuya1,Ichikuni Nobuyuki1ORCID,Masu Hyuma12ORCID,Kanoh Hirofumi3ORCID,Ohara Koji45ORCID,Takahashi Ryunosuke6,Wadati Hiroki67ORCID,Takagi Hideaki8ORCID,Miwa Yohei9ORCID,Kutsumizu Shoichi9ORCID,Kishikawa Keiki1ORCID,Kohri Michinari1ORCID

Affiliation:

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

Abstract

AbstractHere, an unprecedented phenomenon in which 7‐coordinate lanthanide metallomesogens, which align via hydrogen bonds mediated by coordinated H2O 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.

Publisher

Wiley

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