Development of functional materials based on electron-deficient carbon networks

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K05027
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Osaka Institute of Technology
• Principal Investigator: Murata Michihisa 大阪工業大学, 工学部, 准教授 (30447932)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: クロスカップリング / π共役ネットワーク / 蛍光色素 / 有機半導体 / シミュレーション / 超分子 / マテリアル / メカノクロミズム

Outline of Final Research Achievements

We have recently reported short-step synthesis of PAHs that contain a pyracylene moiety, which are based on twofold Scholl cyclization. The thus obtained PAHs exhibit not only an electron-deficient character, but also unique reactivity, which furnished compounds with distinct emission behavior in the solid state. In this research project, we have developed a one-pot domino cross-Scholl reaction in which tetracene reacts with six molecules of benzene to form eight C－C bonds. This intermolecular reaction stands in contrast to the intramolecular Scholl cyclization, which is typically applied to precisely designed precursors. Based on the results of the model reactions and the DFT calculations, a plausible mechanism for the domino reaction, which involves cross-Scholl coupling/annulation and Friedel-Crafts-type reaction, was proposed. This unprecedented reaction should contribute to the short-step synthesis of luminescence materials with intense excimer-type emission.

Free Research Field

有機機能化学

Academic Significance and Societal Importance of the Research Achievements

酸化的C-H/C-Hカップリング反応（Scholl反応）は，π共役ネットワークを合成するための強力な手法である。本研究では，分子間Scholl反応に関して，ベンゼンを試薬として用い，テトラセンに合計6つのベンゼン分子が連続的に反応する分子間ドミノScholl反応を初めて見出した。Scholl反応は，これまで主に分子内反応において強力な威力を発揮すると考えられてきた。分子間の連続反応は長い歴史の中でも前例のないタイプの反応例であり，高い学術的意義をもつものである。今後，前駆体の精密な分子設計とその合成が不要になる可能性も期待されることから，材料科学への貢献において意義のある成果である。