【公開日：2025.06.10】【最終更新日：2025.04.03】
課題データ / Project Data
課題番号 / Project Issue Number
24KT0018
利用課題名 / Title
電子共役型共有結合性フレームワーク分子の規則積層構造
利用した実施機関 / Support Institute
京都大学 / Kyoto Univ.
機関外・機関内の利用 / External or Internal Use
内部利用（ARIM事業参画者以外）/Internal Use (by non ARIM members)
技術領域 / Technology Area
【横断技術領域 / Cross-Technology Area】（主 / Main）計測・分析/Advanced Characterization（副 / Sub）-
【重要技術領域 / Important Technology Area】（主 / Main）次世代ナノスケールマテリアル/Next-generation nanoscale materials（副 / Sub）-
キーワード / Keywords
ナノ多孔体/ Nanoporuous material,電子顕微鏡/ Electronic microscope,メソポーラス材料/ Mesoporous material
利用者と利用形態 / User and Support Type
利用者名（課題申請者）/ User Name (Project Applicant)
Rajendra Paitandi
所属名 / Affiliation
京都大学大学院 工学研究科
共同利用者氏名 / Names of Collaborators in Other Institutes Than Hub and Spoke Institutes
ARIM実施機関支援担当者 / Names of Collaborators in The Hub and Spoke Institutes
小川 哲也
利用形態 / Support Type
（主 / Main）技術代行/Technology Substitution（副 / Sub）-
利用した主な設備 / Equipment Used in This Project
報告書データ / Report
概要（目的・用途・実施内容）/ Abstract (Aim, Use Applications and Contents)
Here we have synthesized a series of radical 2D-covalent organic framework (COF) frameworks in which radical moiety is incorporated within the core of the frameworks and studied their electrical and magnetism behaviour. All these COFs are paramagnetic in nature. We have further utilized these COFs for CO2 adsorption and also for energy storage as Li-S ion batteries.
実験 / Experimental
All these COFs are synthesized by Schiff base condensation reaction of the C3 symmetric radical amine precursor with various electron-accepting aldehyde moieties (C3 symmetric) in the mixture of mesitylene and dioxane at 120°C for 3 days. The crystallinity of these samples are verified by powder X-ray diffraction (PXRD) studies. The formation of the imine linkage is verified by FT-IR studies. The surface area of these COFs is measured by nitrogen adsorption isotherms at 77 K using BET model. The intrinsic charge conductivity of COF sheets was measured using FP-TRMC. Two probes aligned to test static electrical conductivity. The radical nature of the synthesized building blocks and COFs is further confirmed by electron paramagnetic resonance (EPR) spectroscopy.
結果と考察 / Results and Discussion
We have obtained highly crystalline covalent-organic frameworks by optimizing the reaction condition by varying the solvent systems for the synthesis and other parameters (temperature, molar ratio of the building blocks). Mesoporous D-A based radical COF in the "C3+C3" configuration was synthesized through the condensation reactions between donor radical-triamine (C3) and with various C3 symmetric acceptor tri-aldehydes (COF1-3). To investigate the role of planar radical building blocks to obtain highly crystalline and porous COFs we have also synthesised the non-radical COFs using non-planer non-radical building blocks. It was observed that compared to the radical COFs, the obtained non-radical COF is poor crystalline and has low surface area. We further evaluated the interlayer conductivity of this radical COF by flash photolysis time-resolved microwave conductivity (FP–TRMC) measurements. It allows measurement of the inherent charge carrier mobility of the material within several nanometers, after laser pulse irradiation under a rapidly oscillating electric field. As a donor-acceptor structure, this COF showed significant photoconductivity (FSm value) 5.1 × 10–5 cm2 V–1s–1 from the rise and decay transient. Here, f is the charge carrier generation quantum yield and Sm is the sum of the photo-injected charge carrier mobilities of mobile electrons and holes.
図・表・数式 / Figures, Tables and Equations
1
その他・特記事項（参考文献・謝辞等） / Remarks(References and Acknowledgements)
成果発表・成果利用 / Publication and Patents
論文・プロシーディング（DOIのあるもの） / DOI (Publication and Proceedings)
口頭発表、ポスター発表および、その他の論文 / Oral Presentations etc.
特許 / Patents
特許出願件数 / Number of Patent Applications：0件
特許登録件数 / Number of Registered Patents：0件