作为磁性和非线性光开关的热可逆动态键

IF 9.7 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2025-03-17 DOI:10.1007/s11426-024-2512-7

Xue-Li Cao, Jin Liu, Chuan-Qi Shen, Shu-Qi Wu, Zi-Shuo Yao, Qing Li, Zhong-Min Cao, Lu-Yao Liu, Fu-Lin Lin, Zi-Ang Nan, Zhu Zhuo, Wei Wang, Osamu Sato, You-Gui Huang

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引用次数: 0

摘要

一般来说，柔性金属有机框架（mof）通过框架呼吸响应外部刺激（通常是客体吸附和解吸）来改变其结构。在这里，我们展示了柔性MOF中的动态配位键驱动在130-270 K（中心在~ 200 K）的宽温度范围内发生的热诱导扩散相变，从而实现磁性和二次谐波（SHG）响应的切换。具体而言，含联苯-3,3 ',5,5 ' -四羧酸（H4BPTC）和2,2 ':6 '，2″-三吡啶（TPY）配体的无溶剂coii基柔性MOF Co2(TPY)2(BPTC)(1)表现出5倍和6倍可逆的热响应配位模式切换。这种动态键导致了扭曲的极性框架和规则的非极性框架之间的可逆转换，从而导致了磁性能的细微变化和非线性光学性质1的实质性变化。

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A thermally reversible dynamic bond as a magnetic and nonlinear optical switch

In general, flexible metal-organic frameworks (MOFs) change their structures via framework breathing in response to external stimuli (usually guest adsorption and desorption). Here, we show a dynamic coordination bond in a flexible MOF driving a thermo-induced diffuse phase transition occurring in a wide temperature range of 130–270 K (centered at ∼200 K), which enables the switching of magnetism and second-harmonic generation (SHG) responses. In specific, a solvent-free Co^II-based flexible MOF Co₂(TPY)₂(BPTC) (1), bearing biphenyl-3,3′,5,5′-tetracarboxylic acid (H₄BPTC) and 2,2′:6′,2″-terpyridine (TPY) ligands, exhibits a reversible thermo-responsive coordination-mode switching between five- and six-fold. This dynamic bond results in the reversible transformation between a distorted polar framework and a regular nonpolar framework, and therefore leads to the subtle change of the magnetic property and substantial change of the nonlinear optical property of 1.

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.