Precise synthesis of one-dimensional coordination polymers based on sequential axial coordination of dirhodium complexes

2020 Fiscal Year Final Research Report

• Project/Area Number: 18K05219
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 35010:Polymer chemistry-related
• Research Institution: Kyushu University
• Principal Investigator: Morikawa Masa-aki 九州大学, 工学研究院, 助教 (10363384)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Keywords: 一次元配位高分子 / ロジウム二核錯体 / 光異性化 / 刺激応答性

Outline of Final Research Achievements

In this study, supramolecular polymers composed of dirhodium complexes and ditopic axial ligands were synthesized, into which various functional groups were introduced. Control on the monomer sequence, molecular weight, and multi-stimuli response of the coordination polymers was investigated. As a result, we succeeded in synthesizing ABAC-type one-dimensional coordination polymers that were alternately cross-linked with different axial ligands, and succeeded in constructing organized structures according to the monomer sequence. Furthermore, when ring-opening polymerization of a cyclic complex composed of dirhodium complex and ditopic ligand having an azobenzene group was attempted, a structural change from cis-cyclic 1:1 complex to trans-cyclic 2:2 complex was observed. In addition, using a dirhodium complex with oligoether side chains, we succeeded in optical control of LCST behavior, heat-set gelation, and dielectric properties of the drop cast film.

Free Research Field

材料化学

Academic Significance and Societal Importance of the Research Achievements

本研究により、一次元配位高分子における有機配位子の交互配列の方法論が確立され、その一次構造に基づいた組織構造が形成されることを明らかにした。また、環状錯体モノマーの合成と光による環構造の変化を達成したが、開環重合させるためにはより大きな配位エンタルピーが必要であることなど、分子設計指針が示された。さらに、柔軟なオリゴエーテル鎖を導入することにより、水中および固体状態において光・熱・電場など複数の刺激に応答する機能性一次元配位高分子が得られることを明らかにした。