Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets
Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets
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DOI：
10.1021/jacs.9b10584
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发表时间：
2020-01-15
影响因子：
15
通讯作者：
Rigaut, Stephane
中科院分区：
文献类型：
--
作者：
Hojorat, Maher;Al Sabea, Hassan;Rigaut, Stephane
一维配位固体1（c）通过双吡啶基二噻吩基乙烯（DTE）光致变色单元与高度各向异性的镝基单分子磁体[Dy（Tp（py））F（吡啶）（2）] PF 6的反应来合成。缓慢的磁弛豫特性保留在链化合物1（c）中，并且桥接DTE配体的光异构化诱导可以使用光结晶学监测的单晶到单晶的转变。值得注意的是，所得的链状化合物1（o）表现出比1（c）更快的低温弛豫，这在为两种化合物收集的高达4K的磁滞数据中是明显的。从头计算表明，这种光调制的磁弛豫行为是由于晶体包装的变化，而不是改变配体异构化后的晶体场分裂。
A one-dimensional coordination solid 1(c) is synthesized by reaction of a bispyridyl dithienylethene (DTE) photochromic unit with the highly anisotropic dysprosium-based single-molecule magnet [Dy(Tp(py))F(pyridine)(2)]PF6. Slow magnetic relaxation characteristics are retained in the chain compound 1(c), and photoisomerization of the bridging DTE ligand induces a single-crystal-to-single-crystal transformation that can be monitored using photocrystallography. Notably, the resulting chain compound 1(o) exhibits faster low-temperature relaxation than that of 1(c), which is apparent in magnetic hysteresis data collected for both compounds as high as 4 K. Ab initio calculations suggest that this photomodulation of the magnetic relaxation behavior is due to crystal packing changes rather than changes to the crystal field splitting upon ligand isomerization.