Spin Alignment of π-Conjugated Spin Systems Using the Dynamics

使用动力学的 π 共轭自旋系统的自旋对准

基本信息

批准号：
15087208
负责人：
TEKI Yoshio
金额：
$ 23.94万
依托单位：
Osaka City University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2006
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15087208/
关键词：
π-radicals photo-excited high spin state dynamic electron polarization photo-induced spin alignment photo-induced electron transfer ion-pair state time-resolved ESR charge transfer イオン対時間分解ESR 光合成系分子磁性光励起状態スピン整列電子移動エネルギ

项目摘要

In this project, we have obtained the following two representative results.(1)We have obtained the first evidence of the photo-excited quartet state with a unique dynamic electron polarization (DEP) generated through the ion-pair state (charge separated state). The ion-pair state is generated by the intramolecular photo-induced electron transfer from the anthracene moiety to the bodipy functional component. Such a unique DEP pattern has been reported only for the triplet states of the photosystems I, II and the model compounds. This is the first detection of the unique DEP pattern detected in the quartet high-spin state.(2)We have also succeeded to detect a novel lowest photo-excited triplet (S=1) state arising from four unpaired electrons. The low-lying quintet (S=2) photo-excited state was located above the photo-excited triplet state. The unique triplet state has D value reduced by the antiferromagnetic spin alignment between two radical spins through the excited triplet spin coupler. The general theoretical predictions of the spin alignment and the reduction of the fine-structure splitting of the radical-triplet-radical system are presented.In addition to the above results, we investigated several charge-transfer complexes, in which the electron donor parts are the π-radicals with the photo-excited quartet high-spin states. We also clarified the magnetic properties of the some metal complexes using the photo-excited high-spin organic molecules as ligands. Furthermore, we studied the spin dynamics of the photo-excited high-spin states of the π-radicals using a pulsed ESR technique combined with a pulsed LASER excitation.

在这个项目中，我们获得了以下两个代表性成果。（1）我们获得了光激发四重态的第一个证据，该四重态具有通过离子对态（电荷分离态）产生的独特的动态电子极化（DEP）离子对态是通过分子内光诱导电子从蒽部分转移到体二吡啶功能组分而产生的，这种独特的 DEP 模式仅针对光系统的三重态有报道。 I、II 和模型化合物，这是在四重态高自旋态中首次检测到独特的 DEP 模式。(2)我们还成功地检测到了一种新的最低光激发三重态 (S=1) 的产生。低位五重态 (S=2) 光激发态位于光激发三重态之上，独特的三重态的 D 值因反铁磁自旋而降低。通过激发的三重态自旋耦合器实现两个自由基自旋之间的对准，提出了自由基-三重态-自由基系统的自旋对准和精细结构分裂减少的一般理论预测。除了上述结果之外，我们还研究了几个。电荷转移配合物，其中电子供体部分是具有光激发四重高自旋态的π自由基，我们还利用光激发四重态高自旋态阐明了一些金属配合物的磁性。此外，我们使用脉冲 ESR 技术与脉冲激光激发相结合，研究了 π 自由基的光激发高自旋态的自旋动力学。