| 研究課題/領域番号 |
19K21127
|
|---|
| 研究機関 | 大阪大学 |
|---|
研究代表者 |
LU CHAO 大阪大学, 産業科学研究所, 助教 (90828112)
|
|---|
| 研究期間 (年度) |
2019-04-01 – 2023-03-31
|
| キーワード | Excited Ions / Electron Transfer / Laser Flash Photolysis / Physical Chemistry / Photochemistry |
|---|
| 研究実績の概要 |
The purposes of this research project are the clarification of excited-state dynamics and reaction mechanisms of novel excited ion species and the exploration of their application for various systems to establish a new science field of super redox initiators. On the other hand, the fullerene anions have attracted wide interest due to their connection with relevant performances such as the superconductivity of the doped semiconducting materials and the ferromagnetism of fullerene-included devices, etc. In particular, the investigation on the excited dianions (excited bipolarons) of fullerenes and their derivatives is indispensable for exploring the sealed mechanisms of photo-induced processes in related n-type organic conductive materials.
Thus, in the study of this year, C60, C70, and their derivatives including pyrrolidino[60]fullerene (C60-H) and pyrrolidino[70]fullerene (C70-H) were prepared as the target compounds. Theoretical calculations were carried out to illustrate the energy levels and molecular orbital patterns of neutral and dianion species of fullerenes and their derivatives. Femtosecond transient absorption spectroscopy was employed as a main tool to describe the excited dianion characteristics of fullerenes and their derivatives for the first time.
|
| 現在までの達成度 (区分) |
現在までの達成度 (区分)
2: おおむね順調に進展している
理由
In this year's study, fullerene derivatives including C60-H and C70-H have been chemically synthesized. The dianion of trimethylhydroquinone (Me3Q2-) was produced by deprotonation of trimethylhydroquinone with tetrabutylammnioum hydroxide. With a sufficient concentration of Me3Q2-, the selectively generated dianions of fullerenes and their derivatives were confirmed.
The ground- and excited-state fullerene-related dianions were estimated as the singlet states using the DFT/TDDFT calculations despite the previous debate on the spin multiplicity of C602-. By applying the femtosecond laser flash photolysis, the excited-state characteristics of fullerenes and its derivatives have been observed for the first time.
|
| 今後の研究の推進方策 |
Based on the detected excited-state dynamics of fullerene dianions and the related redox potentials, the dyad molecular systems for studying the intramolecular electron transfer from excited dianions as the newly developed super reducing reagents will be designed. Currently, the dyads including C60-pyromellitimide (C60-PI) and C60-naphthalenediimide (C60-NDI) have been chemically synthesized as the target systems. The charge transfer behaviors of the excited divalent ions will be clarified and compared with those of the corresponding excited monoradical ions by using the femtosecond transient absorption spectroscopy.
|
| 次年度使用額が生じた理由 |
The applicant needs to prolong the period of the research project because it is needed more time to carry out the experiments and ensure the realization of the research goals. The usage plan will be mainly focused on the excited states of divalent ions compared with those of the corresponding excited monoradical ions by employing the femtosecond laser measurement.
|
