Komiyama Nao, Ohkubo Takahiro, Maeda Yoshiki, Saeki Yuya, Ichikuni Nobuyuki, Masu Hyuma, Kanoh Hirofumi, Ohara Koji, Takahashi Ryunosuke, Wadati Hiroki, Takagi Hideaki, Miwa Yohei, Kutsumizu Shoichi, Kishikawa Keiki, Kohri Michinari
Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522, Japan.
Center for Analytical Instrumentation, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522, Japan.
Adv Sci (Weinh). 2024 May;11(20):e2309226. doi: 10.1002/advs.202309226. Epub 2024 Mar 13.
Here, an unprecedented phenomenon in which 7-coordinate lanthanide metallomesogens, which align via hydrogen bonds mediated by coordinated HO 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.
通过配位的羟基分子介导的氢键排列的七配位镧系金属介晶,在室温下形成胶束立方中间相,产生体心立方(BCC)型超分子球形阵列。实验和分子动力学模拟结果表明,被无定形烷基域包围的三种配合物的球形组装体以能量稳定的取向自发排列,形成BCC结构。这种现象与六配位金属介晶的传统自组装行为有很大不同,后者由于强分子间相互作用而形成柱状组装体。由于不同镧系元素的磁性和发光特性不同,通过选择合适的镧系元素,可以为球形阵列添加任意功能。本研究中使用七配位镧系金属介晶作为构建单元开发的方法,有望推动胶束立方中间相的合理发展。