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Bpytrisalen/Bpytrisaloph: A Triangular Platform That Spatially Arranges Different Multiple Labile Coordination Sites

  • Takashi Nakamura
    Takashi Nakamura
    Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
  • Yuto Kawashima
    Yuto Kawashima
    Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
  • Eiji Nishibori
    Eiji Nishibori
    Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
  • , and 
  • Tatsuya Nabeshima*
    Tatsuya Nabeshima
    Graduate School of Pure and Applied Sciences and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
    *E-mail: [email protected]
Cite this: Inorg. Chem. 2019, 58, 12, 7863–7872
Publication Date (Web):May 2, 2019
https://doi.org/10.1021/acs.inorgchem.9b00549
Copyright © 2019 American Chemical Society
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Supporting Info (1)»

Abstract

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Complexes that possess multiple metals in their proximity exert useful functions such as multivalent capture and catalytic activities. However, it is often challenging to arrange multiple metals with regular distances and to maintain the reactive coordination sites. We have now designed and synthesized organic macrocyclic ligands, bpytrisalen and bpytrisaloph, as platforms to spatially arrange different kinds of metals and their coordination sites. Metals coordinating to the bpy N2 units of the triangular ligands are assembled in the cavity with their labile coordination sites directed inward. Meanwhile, the metals at the salen/saloph N2O2 units have axial coordination sites that are vertically pointing out of the triangle. As a result, planar homo- and heterohexanuclear complexes with different kinds of coordination sites are obtained. Furthermore, a double-decker structure was selectively constructed upon coordinating a ditopic linker ligand to the axial coordination sites of the salen units, which shows the orthogonality of the coordination sites at the bpy and salen units. The consistency in the array of metal centers and their coordination sites irrespective of the elements is a desirable feature in the pursuit of applications for the multinuclear complexes.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.9b00549.

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Cited By


This article is cited by 9 publications.

  1. Ya-Liang Lai, Xue-Zhi Wang, Xian-Chao Zhou, Rui-Rong Dai, Xiao-Ping Zhou, Dan Li. Self-assembly of a Mixed Valence Copper Triangular Prism and Transformation to Cage Triggered by an External Stimulus. Inorganic Chemistry 2020, 59 (23) , 17374-17378. https://doi.org/10.1021/acs.inorgchem.0c02682
  2. Yingying Ning, Yan Huo, Haozong Xue, Yujing Du, Yuhang Yao, Adam C. Sedgwick, Hengyu Lin, Cuicui Li, Shang-Da Jiang, Bing-Wu Wang, Song Gao, Lei Kang, Jonathan L. Sessler, Jun-Long Zhang. Tri-Manganese(III) Salen-Based Cryptands: A Metal Cooperative Antioxidant Strategy that Overcomes Ischemic Stroke Damage In Vivo. Journal of the American Chemical Society 2020, 142 (22) , 10219-10227. https://doi.org/10.1021/jacs.0c03805
  3. Ya-Juan Li, Shuang-Zhu Guo, Tao Feng, Ke-Feng Xie, Wen-Kui Dong. An investigation into three-dimensional octahedral multi-nuclear Ni(II)-based complexes supported by a more flexible salamo-type ligand. Journal of Molecular Structure 2021, 1228 , 129796. https://doi.org/10.1016/j.molstruc.2020.129796
  4. Takashi Nakamura, Rui Yun Feng, Tatsuya Nabeshima. A Sandwich‐Shaped Hexanuclear Silver Complex with a Giant Cavity Constructed from a Macrocycle with Inward Chelating Units. European Journal of Inorganic Chemistry 2021, 2021 (4) , 308-313. https://doi.org/10.1002/ejic.202000882
  5. Ruo‐Nan Bian, Ji‐Fa Wang, Xin Xu, Xiu‐Yan Dong, Yu‐Jie Ding. Investigation of mononuclear, dinuclear, and trinuclear transition metal (II) complexes derived from an asymmetric Salamo‐based ligand possessing three different coordination modes. Applied Organometallic Chemistry 2021, 35 (1) https://doi.org/10.1002/aoc.6040
  6. Ruo-Nan Bian, Ji-Fa Wang, Ya-Juan Li, Yang Zhang, Wen-Kui Dong. Fluorescent chemical sensor based on double N2O2 cavities for continuous recognition of Cu2+ and Al3+. Journal of Photochemistry and Photobiology A: Chemistry 2020, 403 , 112829. https://doi.org/10.1016/j.jphotochem.2020.112829
  7. Ya-Juan Li, Ruo-Nan Bian, Peng Li, Ke-Feng Xie, Wen-Kui Dong. Investigation of supramolecular assemblies, Hirshfeld surfaces and DFT analyses, and fluorescence properties of three newly synthesized multinuclear Co(II), Ni(II) and Zn(II) complexes. Polyhedron 2020, 192 , 114867. https://doi.org/10.1016/j.poly.2020.114867
  8. Ya-Juan Li, Xin Xu, Ruo-Nan Bian, Ke-Feng Xie, Yang Zhang. Synthesis, structural characterization, fluorescence properties, and DFT calculations of a novel hetero-hexanuclear [Cu II 4 Gd III 2 ] bis(salamo)-like complex involving bidentate chelating and bridging nitrate groups. Inorganic and Nano-Metal Chemistry 2020, 35 , 1-10. https://doi.org/10.1080/24701556.2020.1842450
  9. Xin Xu, Ji-Fa Wang, Ruo-Nan Bian, Li Zhao. Synthesis, structure, Hirshfeld analysis and fluorescence properties of a new asymmetric salamo-based ligand and its Cu(II) complex involving oxime oxygen coordination. Journal of Coordination Chemistry 2020, 73 (15) , 2209-2223. https://doi.org/10.1080/00958972.2020.1822524

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