強発光と高性能単イオン磁性を示す多機能性シアノ架橋型錯体の研究

强发光和高性能单离子磁性多功能氰基交联配合物的研究

• 批准号: 19J22088
• 负责人: WANG JUNHAO
• 金额: $ 1.98万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2019
• 资助国家: 日本
• 起止时间: 2019-04-25 至 2022-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-19J22088/
• 关键词: molecular nanomagnet; luminescence thermometry; luminescence; single molecule magnet; luminescent thermometer; re-absorption effect; photoluminescence; luminescent thermometry; proton-conductivity

This year, following the research objective of searching for novel functional luminescent single-molecule magnets (SMMs) based on lanthanide complexes, I have focused on the magnetic and luminescent studies on a cyanido-bridged d-f bimetallic coordination framework built of Tb(III) and hexacyanocobaltate(III). Single crystal structure study unveiled that this framework can bear a topotactic transformation between an as-synthesized hydrated phase, {[Tb(H2O)2][Co(CN)6] 2H2O}0.7H2O, and its dehydrated phase, Tb[Co(CN)6], reversibly induced by room temperature hydration and thermal dehydration. As a consequence, the functional center, Tb(III) ion, exhibits a switchable characteristics on both magnetic and luminescent properties. Upon dehydration, the Tb complex converts into a highly symmetric trigonal prism geometry, which leads to a very large magnetic anisotropy with Orbach energy barrier over ca. 450 cm^(-1). Such high value is comparable to the very historical yet best Tb(III)- phthalocyaninato SMM system, and we proudly introduce a totally new class of high-performance Tb(III)-SMM in this work. In addition, the Tb-centered luminescence intensity and spectral pattern change due to the variation of ligand field, resulting in a modified optical thermometric characteristic. Notably, the working temperature ranges of SMM behavior and the optical thermometry for the dehydrated phase overlap largely between 6 K to 45 K. Such temperature overlap is to-date the widest, and it opened great possibility of real-time temperature monitoring for the functioning center of a SMM.

今年，根据研究基于灯笼材料复合物的新功能发光单分子磁铁（SMM）的研究目标，我重点介绍了对氰基桥的D-F Bimetallic协调框架的磁性和发光研究，由TB（III）和Hexacyanocobaltate（III）构建。单晶结构研究揭示了该框架可以在AS合成的水合阶段（[TB（H2O）2] [CO（CN）6] 2H2O} 0.7H2O之间进行拓扑转化，其脱水相，TB [CO（CN）6]，通过室温水化和热水水平诱导。结果，功能中心TB（III）离子在磁性和发光特性上都具有可切换特性。脱水后，结核病复合物转化为高度对称的三角棱镜几何形状，从而导致非常大的磁各向异性，而Orbach Energy屏障在Ca上。 450 cm^（-1）。如此高的价值与非常历史但最好的结核病（III） - 邻苯甲酸SMM系统相媲美，我们自豪地在这项工作中引入了一类全新的高性能结核（III）-SMM。此外，由于配体场的变化，以TB为中心的发光强度和光谱图案变化，从而导致了修改的光学温度特征。值得注意的是，SMM行为的工作温度范围和脱水相的光学测光在很大程度上重叠在6 K至45 K之间。这种温度重叠是最宽的，并且为SMM功能中心的实时温度监测开辟了很大的可能性。

项目成果

Cyanido-Bridged {Co-Yb-Co} Supramolecular Network Showing SMM, Luminescence Ratiometric Thermometry, and Proton-conductivity

氰基桥 {Co-Yb-Co} 超分子网络显示 SMM、发光比率测温法和质子电导率

• 发表时间: 2020
• 作者: Junhao Wang;Jakub J. Zakrzewski;Michal Heczko;Mikolaj Zychowicz;Kosuke Nakagawa;Koji Nakabayashi;Barbara Sieklucka;Szymon Chorazy;Shin-ichi Ohkoshi
• 通讯作者: Shin-ichi Ohkoshi

Integrating SMM, luminescent thermometry, porosity, and high proton conductivity within a single molecule-based material

将 SMM、发光测温、孔隙率和高质子电导率集成到单分子材料中

• 发表时间: 2021
• 作者: Junhao Wang;Jakub J. Zakrzewski;Michal Heczko;Mikolaj Zychowicz;Kosuke Nakagawa;Koji Nakabayashi;Barbara Sieklucka;Szymon Chorazy and Shin-ichi Ohkoshi
• 通讯作者: Szymon Chorazy and Shin-ichi Ohkoshi

Novel Approach Towards Luminescent Ratiometric Thermometry Based on the Re-Absorption Effect of Ho(III) Molecular Nanomagnets

基于 Ho(III) 分子纳米磁体重吸收效应的发光比例测温新方法

• 发表时间: 2021
• 作者: Junhao Wang;Jakub J. Zakrzewski;Mikolaj Zychowicz;Koji Nakabayashi;Szymon Choazy and Shin-ichi Ohkoshi
• 通讯作者: Szymon Choazy and Shin-ichi Ohkoshi

Luminescent SMM Showing Proton Conductivity

显示质子电导率的发光 SMM

• 发表时间: 2019
• 作者: Junhao Wang;Mikolaj Zychowicz;Michal Heczko;Koji Nakabayashi;Kosuke Nakagawa;Szymon Chorazy and Shin-ichi Ohkoshi
• 通讯作者: Szymon Chorazy and Shin-ichi Ohkoshi

Holmium(III) SMMs Functioning as Optical Thermometers Based on Luminescence Re-Absorption Effect

基于发光重吸收效应的钬(III) SMM 光学温度计

• 发表时间: 2021
• 作者: Junhao Wang;Jakub J. Zakrzewski;Mikolaj Zychowicz;Veacheslav Vieru;Liviu Chibotaru;Koji Nakabayashi;Szymon Chorazy and Shin-ichi Ohkoshi
• 通讯作者: Szymon Chorazy and Shin-ichi Ohkoshi