Kong Hui, Wang Jing-Yu, Liu Jia-Chuan, Zhang Lu, Liao Pei-Yu, Qi Yu-Quan, Liu Zheng, Wu Si-Guo, Tong Ming-Liang
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, Sun Yat-Sen University, Guangzhou, 510006, P. R. China.
Angew Chem Int Ed Engl. 2025 Mar 17;64(12):e202422557. doi: 10.1002/anie.202422557. Epub 2025 Jan 2.
A photochromic dysprosium-based single-molecule magnet Dy(CyPhPO)(HO) ⋅ 3CyPhPO⋅HO (1-Dy) is synthesized via cocrystal engineering of a polyoxomolybdate (POMo) anion and an Ising-type cation with pseudo pentagonal bipyramidal geometry. Upon ultraviolet irradiation, Mo-to-Mo single-electron photoreduction occurs in the POMo moiety, resulting in significant changes of optical and magnetic properties. The emergence of intervalence charge-transfer transitions in heteropoly blue state 1-Dy* facilitates photothermal conversion in near-infrared region. Meanwhile, the coercive field of hysteresis loop is altered from 0.72 T (1-Dy) to 0.04 T (1-Dy*) at 2 K, which might be contributed to the magnetic interaction between Dy and Mo. After dark treatment, 1-Dy* can convert to the initial state with the recovery of magnetic memory effect. These results presented herein provide a blueprint for developing versatile opto-magnetic materials via the coupling of photochemical regulation and magnetic interaction.
通过多金属氧酸盐（POMo）阴离子和具有伪五角双锥几何结构的伊辛型阳离子的共晶工程，合成了一种基于光致变色镝的单分子磁体Dy(CyPhPO)(HO) ⋅ 3CyPhPO⋅HO（1-Dy）。在紫外线照射下，POMo部分发生Mo到Mo的单电子光还原，导致光学和磁性发生显著变化。杂多蓝态1-Dy中介于价态间的电荷转移跃迁的出现促进了近红外区域的光热转换。同时，在2 K时，磁滞回线的矫顽场从0.72 T（1-Dy）变为0.04 T（1-Dy），这可能归因于Dy和Mo之间的磁相互作用。经过暗处理后，1-Dy*可以恢复到初始状态，并恢复磁记忆效应。本文给出的这些结果为通过光化学调控和磁相互作用的耦合开发多功能光磁材料提供了蓝图。
