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Light-induced stepped thermal relaxation in a Hofmann-type metal-organic framework

Science China Chemistry 2024年第6期67卷 1983-1989页

作者： Wen Cui Wei-Wei Wu Ze-Yu Ruan Yan-Cong Chen Guang-Jun Zeng Guan-Xi Chen Si-Guo Wu Zhao-Ping Ni Ming-Liang Tong Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education School of ChemistryInstitute of Green Chemistry and Molecular EngineeringGuangdong Basic Research Center of Excellence for Functional Molecular EngineeringSun Yat-sen UniversityGuangzhou510275China

Spin-crossover(SCO)materials with light-induced multistability have potential applications in multi-addressable opto-magnetic memory devices and multiple switches.Here,we reported a three-dimensional Hofmann-type metal-organic framework(MOF)[Fe(bpy){Pt(CN)_(4)}]·coumarin(1·coumarin,bpy=4,4′-bipyridine),which exhibits an incomplete and hysteretic SCO behavior.Most importantly,the light-induced stepped thermal relaxation(LISTR)with obvious magnetic plateau for a hidden intermediate spin state is firstly realized.This hidden spin state is also observed for the first time in the thermal relaxation after light-assisted spin state annealing(LASSA).Meanwhile,an extremely rare bi-directional light-induced excited spin-state trapping(LIESST)with the highest reverse-LIESST temperature is observed.Therefore,five spin states can be captured in 1·coumarin and the tristability can be modulated below 102 K through the excitation-relaxation mechanism.Hence,the light-and temperatureinduced multistability provides a new strategy for developing multistable materials.

关键词： light magnetic multistability iron metal-organic framework spin-crossover

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A trinuclear {Fe_(2)^(Ⅲ)Fe^(Ⅱ)} complex involving both spin and non-spin transitions exhibits three-step and wide thermal hysteresis

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Science China Chemistry 2022年第3期65卷 532-538页

作者： Xin-Hua Zhao Dong Shao Jia-Tao Chen De-Xuan Gan Jiong Yang Yuan-Zhu Zhang Department of Chemistry Southern University of Science and Technology(SUSTech)Shenzhen 518055China

The engineering of switchable molecules with magnetic multistability is lying on the cutting-edge research topics for integrating multi-switches and ternary memory devices. Here we presented a cyanide-bridged {Fe_(2)^(Ⅲ)Fe^(Ⅱ)} desolvated complex {[(pzTp)Fe^(Ⅲ)-(CN)3]2[Fe^(Ⅱ)(L)]} (1), obtained through single-crystal-to-single-crystal (SCSC) transformation from its solvated phase {[(pzTp)-Fe^(Ⅲ)(CN)3]2[Fe^(Ⅱ)(L)]}·2CH_(3)OH·5H_(2)O (1·sol). Remarkably, 1 exhibited unprecedented three-step transition in magnetization with wide thermal hysteresis (44, 40, and 36 K) in the temperature range of 80–320 K. The detailed studies demonstrated that the tristable character originates from both an order-disorder structural phase transition (SPT) and a strongly cooperative two-step spin crossover (SCO) process. This work thus provides a new promising strategy for realizing multiple bistablity in magnetization by introducing two different transitions.

关键词： magnetic multistability cyanide complex spin crossover phase transition magnetic switching

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