Establishment of a method for designing dimerization behavior of dynamic covalent radicals

2023 Fiscal Year Final Research Report

• Project/Area Number: 20H02726
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Osaka Metropolitan University (2022-2023); Osaka Prefecture University (2020-2021)
• Principal Investigator: Sakamaki Daisuke 大阪公立大学, 大学院理学研究科, 准教授 (60722741)
• Co-Investigator(Kenkyū-buntansha): 藤原 秀紀 大阪公立大学, 大学院理学研究科, 教授 (70290898)
• Project Period (FY): 2020-04-01 – 2024-03-31
• Keywords: 有機ラジカル / 動的共有結合 / 二量化 / 配位結合

Outline of Final Research Achievements

Covalent bonds, in which bond formation and cleavage are reversibly repeated, are called dynamic covalent bonds and are expected to be applied to the construction of molecular self-assembling systems and self-healing materials. Among them, the reversible dimerization-cleavage reaction of radicals has recently attracted much attention as the simplest motif of dynamic covalent bonding because it does not involve catalysts or by-products. We have demonstrated that linking an electron-donating substituent, such as an amine, to a dicyanomethyl radical leads to highly reversible dynamic covalent bonding. In this study, we extended this knowledge to the development of dynamically covalent radicals with redox and coordination bonding abilities.

Free Research Field

構造有機化学

Academic Significance and Societal Importance of the Research Achievements

これまでに動的共有結合性を示すラジカルは数多く知られていたが、配位結合や水素結合などの共有結合とは別種の相互作用を、可逆的な共有結合形成-開裂と同時に示すラジカルは知られていなかった。本研究で我々は、ピリジルアミノ基と共役したジシアノメチルが、パラジウムイオンへの配位結合と動的な共有結合の両方を示すことを実証した。この結果から、ラジカルの可逆な結合開裂と金属イオンへの錯形成-解離が互いを邪魔せずに両立することが示され、新たな分子材料の開発指針となると考えられる。