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Electron transfer photochromism of Ln-based (Ln = Dy, Tb) coordinated polymers for reversibly switching off/on single-molecule magnetic behavior

Ln基(Ln = Dy, Tb)配合物的电子转移光致变色及其可逆开关单分子磁体行为

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Abstract

Switching on/off single-molecule magnets (SMMs) at room temperature is still a challenge in moleculebased magnets. Herein, two photochromic Ln-based (Ln = Dy, Tb) phosphonate coordinated polymers were synthesized with regulable SMM behavior. The reversible room-temperature photo-coloration was an electron transfer process with a generation of relatively stable radicals, characterized by structural analyses, ultraviolet-visible, luminescence and electron spin resonance spectra and magnetic measurements. Importantly, owing to the antiferromagnetic coupling interactions between Ln3+ ions and photogenerated radicals, the room-temperature light irradiation surprisingly switched off the SMM behavior, showing the first example of radicalquenched SMMs in the molecule-based magnets. Moreover, the silient SMM behavior could be recovered after eliminating photogenerated radicals via heat treatment, showing a reversible off/on switch of SMMs via light and heat. This work constructs a system for switching off/on SMMs through electron transfer photochromism, providing a visual operation way via naked-eye-detectable coloration for the switchable SMMs.

摘要

室温下实现单分子磁体(SMM)的开关行为仍然是分子磁体研究 中的一个挑战. 本文合成了两例具有SMM行为的光致变色Ln基(Ln = Dy, Tb)膦酸盐配合物. 结构分析、紫外-可见光谱、发光光谱、电子 自旋共振光谱和磁性测量等手段共同表明, 目标产物的室温可逆光致 变色行为是光生自由基诱导的电子转移过程. 重要的是, 由于Ln3+与光 生自由基间的反铁磁耦合作用, 首次观测到室温光照可猝灭SMM行为. 此外, 通过热处理消除光生自由基后, SMM的行为得以恢复, 因而通过 光照和加热实现了可逆的SMM关/开变化. 本工作在电子转移光致变色 体系中实现SMM的可控开/关, 为可调控的SMM提供了一种可视化的 操作方式.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21901133, 22171155 and 22071126) and the State Key Laboratory of Fine Chemicals (KF 1905).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, 266071, China

    Qian Zhang  (张倩), Song-De Han  (**松德), Qi Li  (**琪), Ji-**ang Hu  (胡继祥) & Guo-Ming Wang  (王国明)

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  1. Qian Zhang  (张倩)
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  2. Song-De Han  (**松德)
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  3. Qi Li  (**琪)
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  4. Ji-**ang Hu  (胡继祥)
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  5. Guo-Ming Wang  (王国明)
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Contributions

Zhang Q, Han SD and Li Q performed the experiments; Hu JX, Zhang Q and Han SD performed the data analysis; Hu JX wrote the paper; Hu JX and Wang GM designed the concept and supervised the experiments. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Ji-**ang Hu  (胡继祥) or Guo-Ming Wang  (王国明).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper. CCDC 2097403 and 2097404 for 1 and 2 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Qian Zhang was born in 1997 in Shandong, China. She obtained her BSc degree from Qingdao University in 2019. Now she is a master student under the supervision of Prof. Guo-Ming Wang. Her research is focused on the exploration of the photochromic properties of metal phosphonates.

Song-De Han was born in 1987 in Shandong, China. He received his BSc degree from Qingdao University in 2010, and PhD degree (2015) in chemistry from Nankai University under the supervision of Prof. **an-He Bu. In 2015, he joined the faculty of Qingdao University. He is currently an associate professor at the College of Chemistry and Chemical Engineering. His current research interests include the design and synthesis of crystalline hybrid materials with focus on photochromism, and room-temperature phosphorescence.

Qi Li was born in 1997 in Shandong, China. She obtained her BSc degree from Qingdao University in 2019. Now she is a master student under the supervision of Prof. Ji-**ang Hu. Her research focuses on the design and construction of photomagnetic systems.

Ji-**ang Hu was born in 1988 in Shandong, China. He earned his PhD degree (2018) in chemistry from Dalian University of Technology under the supervision of Prof. Tao Liu. In 2018, he joined Qingdao University and became a full professor. His research interests are related to the design and synthesis of photomagnetic molecules and spin crossover complexes, and the dynamic control of the hybrid materials.

Guo-Ming Wang was born in 1977 in Shandong, China. He obtained his PhD degree from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (CAS) in 2005 under the supervision of Prof. Guo-Yu Yang. In 2006, he joined Qingdao University and became a full professor in 2012. His current research interest focuses on the design and synthesis of crystalline framework materials with room-temperature phosphorescence, photochromism, photomagnetism and other photo-modulated physical properties.

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40843_2021_1896_MOESM1_ESM.pdf

Electron transfer photochromism of Ln-based (Ln = Dy, Tb) coordinated polymers for reversibly switching off/on single-molecule magnetic behavior

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Zhang, Q., Han, SD., Li, Q. et al. Electron transfer photochromism of Ln-based (Ln = Dy, Tb) coordinated polymers for reversibly switching off/on single-molecule magnetic behavior. Sci. China Mater. 65, 788–794 (2022). https://doi.org/10.1007/s40843-021-1896-6

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