スピロ炭素戦略を用いた立体規則性共役系高分子の創製

使用螺碳策略创建有规立构共轭聚合物

• 批准号: 15J05745
• 负责人: 徐 錦嘉
• 金额: $ 1.09万
• 依托单位: National Institute for Materials Science (2016)University of Tsukuba (2015)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2015
• 资助国家: 日本
• 起止时间: 2015-04-24 至 2017-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15J05745/
• 关键词: macrocyclization; bifluorenyldene; electron acceptors; twisted but conjugated; 立体規則性; 共役系高分子; ヘリシティ

a) I successfully established a straightforward approach to synthesize the highly strained 9,9’-bifluorenylidene cyclic dimer (CBF) from 9,9’-bifluorenylidene (BF) by unexpected intramolecular cyclization via typical Yamamoto coupling reaction conditions. Sequential Yamamoto coupling reactions potentially allowed us to obtain well-defined and highly twisted but conjugated 9,9'-BF ladder tetramer (LBF).b) The photophysical and electrochemical properties of BF and CBF were systematically investigated by using UV-vis absorption and CV measurements. The BF and CBF were demonstrated to have ability to accept two electrons, probably favored by release of steric hindrance from proximal aromatic rings and development of a 14- electron system.c) The thermal behavior and phase transition processes of BF and CBF was determined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Characterization by DSC reveals no phase transitions between 25°C and 200°C for CBF, presumedly due to the existence of enantiomeric mixture namely (P, P) and (M, M), yielding CBF more amorphous than crystalline. In stark contrast, BF showed the broadening melting point at around 153°C in the second heating process, probably attributable to multi-conformations from BF. Surprisingly, in the cooling process, one sharp peak at 150°C in additional to one small peak at 154°C was observed, thus we infer that multiple phase transitions occur sequentially by alternating the conformation of BF.

a）我成功地建立了一种直接的方法，可以通过典型的典型Yamamoto couppling反应条件，通过意外的分子循环来合成9,9'-二氟苯基（BF）的高度紧张的9,9'-二甲基二烯环二聚体（CBF）。顺序的Yamamoto耦合反应可能使我们获得了明确的，高度扭曲但共轭的9,9'BF梯子四聚体（LBF）.B）BF和CBF的光体物理和电化学性质，使用UV-Vis-Vis-Vistaction和CV测量进行了系统地研究。 BF和CBF已被证明具有接受两种电子的能力，这可能是通过从近端芳族环中释放的空间障碍和14电子系统的开发而受到青睐的。通过DSC的表征显示，CBF的25°C和200°C之间没有相变，由于存在对映体混合物（P，P）和（M，M），因此呈现出比晶体更无定形的CBF。与之形成鲜明对比的是，在第二个加热过程中，BF在153°C左右显示出宽阔的熔点，这可能归因于BF的多种构造。出乎意料的是，在冷却过程中，在150°C下在150°C下的一个尖峰观察到154°C时的一个小峰，因此我们推断出多个相变的依次通过改变BF的构象来依次发生。

项目成果

Multiple emissions from indenofluorenedione in solution and polymer films

• DOI: 10.1039/c6ra17765d
• 发表时间: 2016-08
• 期刊: RSC Advances
• 影响因子: 3.9
• 作者: Jinjia Xu;Atsuro Takai;M. Takeuchi

Full Color Fluorescence From RGB Trichromophoric Nanoparticle System Assisted by Dual-FRET in Aqueous Medium Towards Visual Bio-sensing

水介质中双 FRET 辅助下 RGB 三色纳米粒子系统的全色荧光迈向视觉生物传感

• 发表时间: 2015
• 作者: J. Xu;A. Takai;M. Takeuchi
• 通讯作者: M. Takeuchi