Strategic Exploration of Quinoline-Based Materials

喹啉基材料的战略探索

• 批准号: 22K14670
• 负责人: XU Wei
• 金额: $ 3万
• 依托单位: Keio University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Early-Career Scientists
• 财政年份: 2022
• 资助国家: 日本
• 起止时间: 2022-04-01 至 2024-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-22K14670/
• 关键词: metal complex; quinoline; saddle shape; macrocycle; tetradentate; oligomer; catalysis; fluorescence

We have designed and synthesized TEtraQuinoline (TEQ), a new family of conjugated macrocycles containing four inwardly oriented nitrogen atoms, which exhibit a rigid saddle-shape structure and special chemical and physical properties. TEQ is synthesized from a cyclic dimer of quinoline-amide substrate and an alkyne in the presence of Tf2O and pyridine derivatives. DFT calculations are carried out to gain a deeper understanding of the reaction mechanism.The C2-symmetric substituted TEQ has a considerably high energy barrier for flipping to secure its chirality, which has been experimentally confirmed by no erosion of the enantiomeric excess even at 240 °C. TEQ accommodates various types of transition metal cations, such as Fe2+, Co2+, Ni2+, Cu2+, Zn2+ and Pd2+, to form corresponding metal complexes, which displayed high kinetic stability toward cation exchange and protonation. The structure of these complexes are undoubtedly confirmed by X-ray crystallography, and a TEQ-Fe(II) complex exhibits catalytic activity in dehydrogenation reactions with catalyst loadings as low as 0.1 mol%. TEQ shows inherently weak fluorescence, and it becomes strongly emissive upon protonation or addition of upon protonation or addition of Zn(II) cations, suggesting potential application as structurally robust pH or Zn probes.

我们设计并合成了四喹啉（TEQ），这是一类新的含四个氮原子的共轭大环化合物，具有刚性的鞍形结构和特殊的物理化学性质。TEQ是由喹啉-酰胺底物和炔在Tf 2 O和吡啶衍生物存在下的环状二聚体合成的。通过密度泛函理论（DFT）计算，我们对反应机理有了更深入的了解。C2对称取代的TEQ具有相当高的翻转能垒，以确保其手性，这一点已被实验证实，即使在240 °C下也没有对映体过量的侵蚀。TEQ可容纳各种类型的过渡金属阳离子，如Fe 2+，Co 2+，Ni 2+，Cu 2+，Zn 2+和Pd 2+，形成相应的金属配合物，其对阳离子交换和质子化表现出高动力学稳定性。这些配合物的结构无疑证实了X-射线晶体学，和TEQ-Fe（II）配合物表现出催化活性的脱氢反应与催化剂负载低至0.1摩尔%。TEQ显示出固有的弱荧光，并且它在质子化或添加Zn（II）阳离子后变得强烈发射，表明作为结构上稳健的pH或Zn探针的潜在应用。

项目成果

キノリン及びナフタレンを構成単位とする環状4量体の合成と物性

以喹啉和萘为结构单元的环状四聚体的合成及物理性质

• 发表时间: 2023
• 作者: 野仲はる;Wei Xu;熊谷直哉
• 通讯作者: 熊谷直哉

TEtraQuinoline (TEQ) and Other Cyclic Quinoline Oligomers, a New Family of Macrocycles

四喹啉 (TEQ) 和其他环状喹啉低聚物，一个新的大环家族

• 发表时间: 2023
• 作者: Wei Xu;Haru Nonaka;Ryota Yagami;Mizuki Nishiwaki;Ayami Takeda;Naoya Kumagai
• 通讯作者: Naoya Kumagai

Design, Synthesis, Properties of TEtraQuinoline (TEQ) and Its Application as Zinc Cation Fluorescent Probe

四喹啉(TEQ)的设计、合成、性质及其作为锌阳离子荧光探针的应用

• 发表时间: 2022
• 作者: Wei Xu;Naoya Kumagai
• 通讯作者: Naoya Kumagai

キノリン/インドール環状4量体（Q2In2）のデザイン・合成および物性評価

喹啉/吲哚环状四聚体（Q2In2）的设计、合成及物性评价

• 发表时间: 2023
• 作者: 木原和輝;木村美玲;Wei Xu;熊谷直哉
• 通讯作者: 熊谷直哉

一原子欠損π平面環状分子トリキノリン誘導体DQMQzの新規合成法とその機能展開

缺单原子π平面环状分子三喹啉衍生物DQMQz的新合成方法及其功能开发

• 发表时间: 2023
• 作者: 狩俣太雅;Wei Xu;山崎洋子;熊谷直哉
• 通讯作者: 熊谷直哉