Theoretical elucidation of formation processes of infinite self-assembled structures of coordination polymers without experimental inference

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K18970
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
• Research Institution: Nagoya University (2023); Hokkaido University (2021-2022)
• Principal Investigator: Hijikata Yuh 名古屋大学, 未来社会創造機構, 特任准教授 (70622562)
• Project Period (FY): 2021-07-09 – 2024-03-31
• Keywords: 自己集積 / 理論計算 / 多孔性配位高分子

Outline of Final Research Achievements

The purpose of this project was theoretical elucidation of the self-assembly processes of coordination polymers, which are assembled by the self-assembly of metal ions and organic ligands, through comprehensive searches of reaction pathways. The following points were elucidated concerning the formation process of building units of coordination polymers.
1. Equilibrium reaction processes with low energy barriers exist as intermediate states, and a building unit is formed through these intermediate states. 2. The stability of building unit precursors depends on metal species, and stabilization of building unit precursors by solvent molecules and exchange reactions of solvent molecules with ligands are important. The formation process and determining factors depend on the metal species even though the formed unit structures are the same.
These factors were understood by only experimental chemical intuition, and this theoretical research were able to elucidate them.

Free Research Field

理論計算化学

Academic Significance and Societal Importance of the Research Achievements

本理論研究における結果は，配位高分子の合成研究において感覚的に捉えられていた反応機構を明らかにするだけでなく，組み上がる骨格は同形であっても金属種によって骨格形成の中間体の安定性が異なり，結果として骨格形成過程も異なることまで明らかにした．これによって，今まで自己集積としてのみ説明してきた反応過程の理解が進み，配位高分子合成の真の設計指針に資する知見を与えるものである．