光驱动的金属富勒烯分子磁开关※

doi:10.6023/A21120564

化学学报 ›› 2022, Vol. 80 ›› Issue (2): 101-104.DOI: 10.6023/A21120564 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究通讯

光驱动的金属富勒烯分子磁开关^※

吴波^a^,^b^,^*(), 王冲^a^,^b, 李宝林^a^,^c, 王春儒^a^,^b

a 中国科学院化学研究所北京分子科学国家研究中心分子纳米结构与纳米技术重点实验室北京 100190
b 中国科学院大学化学科学学院北京 100049
c 内蒙古大学化学化工学院呼和浩特 010030

投稿日期:2021-12-15 发布日期:2022-01-20
通讯作者: 吴波
作者简介:
^※庆祝中国科学院青年创新促进会十年华诞.
基金资助:
国家自然科学基金(52072374); 国家自然科学基金(51772300); 国家自然科学基金(51832008); 中国科学院青年创新促进会(2018039)

Light-driven Molecular Magnetic Switch for a Metallofullerene^※

Bo Wu^a^,^b(), Chong Wang^a^,^b, Baolin Li^a^,^c, Chunru Wang^a^,^b

a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
c School of Chemistry & Chemical Engineering, Inner Mongolia University, Huhhot 010030, China

Received:2021-12-15 Published:2022-01-20
Contact: Bo Wu
About author:
^※Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Natural Science Foundation of China(52072374); National Natural Science Foundation of China(51772300); National Natural Science Foundation of China(51832008); Youth Innovation Promotion Association of CAS(2018039)

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1. Supporting Information-A21120564.pdf(679KB)

摘要/Abstract

由于碳笼的保护, 从外部操控内嵌富勒烯笼内分子的特性一直是一个挑战. 通过在顺磁性金属富勒烯Sc₃C₂@C₈₀碳笼外修饰具有光活性的偶氮苯-氮氧自由基, 成功设计出基于金属富勒烯-氮氧自由基的分子开关, 实现了原位可逆地光驱动远程控制金属富勒烯的顺磁特性. 在不同光照条件下, 利用偶氮苯的光异构化特性改变双自旋中心的相对位置, 调整自旋-自旋、自旋-晶格相互作用, 进而影响金属富勒烯的电子顺磁特性. 研究发现, 紫外光照下, 氮氧自由基使金属富勒烯Sc₃C₂@C₈₀的顺磁信号逐渐减弱, 可见光照下Sc₃C₂@C₈₀的顺磁信号又增强, 由此实现了氮氧自由基作为顺磁开关的功能.

关键词: 金属富勒烯, 偶氮苯, 氮氧自由基, 光致异构, 分子开关

Metallofullerene Sc₃C₂@C₈₀was synthesized by the arc-discharging method and isolated by multi-stage high performance liquid chromatography. Two Sc₃C₂@C₈₀ azobenzene nitroxide radical derivatives, compound I and II were synthesized through a Prato reaction, respectively. Usually, azobenzene undergoes trans-cis isomerization when irradiated with light tuned to an appropriate wavelength. The reverse cis-trans isomerization can be driven by light or occurs thermally in the dark. Thus, the compound I was excited by UV light, and it exhibited a strong absorption band decrease at around 340 nm and a slight increase at about 470 nm, which belonging to the π→π* and n→π* transition respectively. Similar to the azobenzene molecule in solution, the typical change of the absorption spectrum of compound I can be ascribed to the trans-to-cis transition with UV light irradiation. Similarly, the reverse isomerization of UV-irradiated compound I with visible light (475 nm) resulted in an obvious π→π* band increase, also indicating the reverse isomerization of compound I from cis-to-trans form. Besides, the structure and spin density distributions of compound I were calculated as well. It has two unpaired spins localizing on the Sc₃C₂@C₈₀ moiety and nitroxide radical. The magnetic property of metallofullerene can be manipulated by the spin interactions of the two spin centers. The electron paramagnetic resonance (EPR) signals of the trans isomer of the compound I are almost independent of each other. After UV light irradiation, the distance of the two spin centers decreased to r=0.752 nm, and the strong spin-spin interaction weakened the EPR signals of Sc₃C₂@C₈₀. However, the decreased chain length between Sc₃C₂@C₈₀ and nitroxide radical would result in a weakened spin-lattice interaction, which increased the EPR signals of the nitroxide radical. Moreover, the UV-radiated compound I with visible light treated later for several minutes, and the EPR signals of Sc₃C₂@C₈₀ has a certain degree of recovery with visible light irradiation. Therefore, the compound I has sensitive and reversible spin variation with different light irradiation. The remote nitroxide radical group serves as a magnetic switch for the EPR signal of Sc₃C₂@C₈₀ through the photoisomerization properties of azobenzene bridge. The EPR signals of Sc₃C₂@C₈₀ moiety were decreased by the strong spin-spin interaction, and the EPR signals of Sc₃C₂@C₈₀ would be enhanced by larger space with visible light irradiation. Such magnetic switch for metallofullerenes has potential applications in quantum information processing and molecular devices.

Key words: metallofullerene, azobenzene, nitroxide radical, photoisomerization, molecular switch

引用此文

吴波, 王冲, 李宝林, 王春儒. 光驱动的金属富勒烯分子磁开关^※[J]. 化学学报, 2022, 80(2): 101-104.

Bo Wu, Chong Wang, Baolin Li, Chunru Wang. Light-driven Molecular Magnetic Switch for a Metallofullerene^※[J]. Acta Chimica Sinica, 2022, 80(2): 101-104.

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图/表 5

图1. 化合物I和II的结构及化合物I的自旋密度分布

Figure 1. The constructions of compound I, II and the spin density distributions of compound I (a) The synthesis of metallofullerene derivative compound I and II. (b) The calculated structure and spin density distributions of the compound I, and the reversible transformation of trans and cis isomer. The distance of the two spin centers in the trans form is about 2.048 nm, and the cis form is 0.752 nm

图2. 紫外光照不同时间的紫外-可见吸收光谱变化

Figure 2. The variation of UV/Vis spectra upon irradiation with UV light for different time UV/Vis spectra of (a) N=N-TEMPO (1a) and (b) compound I upon irradiation with UV light for different time. Arrows clarify the trends of the spectral changes. Inset: enlargement of the signal at 420~500 nm, and 470~550 nm

图3. 化合物I在紫外光照前后的EPR光谱

Figure 3. The EPR spectra of compound I in pristine state and after UV light irradiation (a) The EPR spectra and (b) integral of compound I in pristine state (black) and after irradiated with UV light for 24 min (red)

图4. 化合物I在光照射后的紫外-可见吸收光谱和EPR光谱

Figure 4. The UV/Vis spectra and time-dependent EPR spectra of compound I at UV or visible light irradiation (a) UV/Vis spectra of compound I upon irradiation with visible light after UV-irradiated 24 min. Arrows clarify the trends of the spectral changes. (b) Time-dependent EPR spectra of compound I at variable UV or visible light irradiation in toluene solution at argon atmosphere

图5. 化合物I反式和顺式构型的循环可逆EPR信号变化

Figure 5. The EPR signals of the compound I in trans and cis configuration with UV or visible light irradiation reversible Cyclic and reversible transitions of the compound I in trans and cis configuration with UV or visible light irradiation. The EPR signal (3200.8 G) intensity changes under different conditions

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光驱动的金属富勒烯分子磁开关^※

Light-driven Molecular Magnetic Switch for a Metallofullerene^※

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光驱动的金属富勒烯分子磁开关※

Light-driven Molecular Magnetic Switch for a Metallofullerene※

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光驱动的金属富勒烯分子磁开关^※

Light-driven Molecular Magnetic Switch for a Metallofullerene^※