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，本着寻找基于镧系配合物的新型功能发光单分子磁体（SMMs）的研究目标，我重点研究了由Tb（III）和六氰钴酸盐（III）构建的氰基桥接d-f双金属配位框架的磁性和发光研究。单晶结构研究表明，该框架可承受室温水化和热脱水可逆诱导的水化相{[Tb(H2O)2][Co(CN)6] 2H2O}0.7H2O与脱水相Tb[Co(CN)6]之间的拓扑结构转变。因此，功能中心，Tb（III）离子，在磁性和发光性质上都表现出可切换的特征。脱水后，Tb配合物转变为高度对称的三角棱镜几何结构，这导致了一个非常大的磁各向异性，奥尔巴赫能垒超过约450 cm^（-1）。如此高的价值可与历史上最好的Tb(III)-酞菁酸酯SMM系统相媲美，我们自豪地在这项工作中介绍了一种全新的高性能Tb(III)-SMM。此外，由于配体场的变化，tb中心的发光强度和光谱模式发生了变化，导致光学测温特性发生了改变。值得注意的是，SMM行为的工作温度范围和脱水相的光学测温范围在6 ~ 45 K之间有很大的重叠。这种温度重叠是迄今为止最广泛的，为SMM功能中心的实时温度监测提供了可能。

项目成果

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

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

Multifunctionalities of Proton-conductivity Luminescence and Single Molecule Magnetism in {YbCo_2} supramolecular network

{YbCo_2}超分子网络中质子电导发光和单分子磁性的多功能性

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

Tunable magnetic anisotropy in luminescent cyanido-bridged {Dy2Pt3} molecules incorporating heteroligand PtIV linkers

结合异质配体 PtIV 连接体的发光氰基桥接 {Dy2Pt3} 分子中的可调磁各向异性

• DOI: 10.1039/d1dt03071j
• 发表时间: 2021
• 期刊: Dalton Transactions
• 影响因子: 4
• 作者: Puzan Agnieszka;Zychowicz Mikolaj;Wang Junhao;Zakrzewski Jakub J.;Reczynski Mateusz;Ohkoshi Shin-ichi;Chorazy Szymon
• 通讯作者: Chorazy Szymon