Department of Chemistry, University of Florida , Gainesville, Florida 32611-7200, United States.
J Am Chem Soc. 2014 Jul 16;136(28):9846-9. doi: 10.1021/ja504289p. Epub 2014 Jun 30.
Coordination polymer thin film heterostructures of the Prussian blue analogue Ni(II)bCr(III)(CN)6·nH2O (NiCr-PBA) and the 3D Hofmann-like spin crossover compound Fe(azpy)[Pt(CN)4]·xH2O {azpy = 4,4'-azopyridine} have been developed, and spin transition properties have been characterized via SQUID magnetometry and Raman spectroscopy. The magnetic response of the ferromagnetic NiCr-PBA layer (T(c) ≈ 70 K) can be altered by inducing the LIESST effect (light-induced excited spin state trapping) in the coupled paramagnetic Fe(II) spin crossover material. Whereas an increase in magnetization is measured for the single-phase Fe(azpy)[Pt(CN)4]·xH2O, a decrease in magnetization is observed for the heterostructure. These results indicate the LIESST effect alone cannot account for the sign and magnitude of the magnetization change in the heterostructure, but the temperature profile of the magnetization shows that significant changes in the NiCr-PBA network are correlated to the spin state of the Hofmann-like SCO network.
已经开发出普鲁士蓝类似物 Ni(II)bCr(III)(CN)6·nH2O(NiCr-PBA)和 3D Hofmann 类似自旋交叉配合物 Fe(azpy)[Pt(CN)4]·xH2O(azpy=4,4'-联吡啶)的配位聚合物薄膜异质结构,并通过 SQUID 磁强计和拉曼光谱对自旋跃迁性质进行了表征。在耦合的顺磁 Fe(II)自旋交叉材料中诱导 LIESST 效应(光致激发自旋态捕获)可以改变铁磁 NiCr-PBA 层的磁响应(T(c)≈70 K)。虽然单相 Fe(azpy)[Pt(CN)4]·xH2O 的磁化强度增加,但异质结构的磁化强度却降低。这些结果表明,LIESST 效应本身不能解释异质结构中磁化强度变化的符号和幅度,但磁化强度的温度曲线表明 NiCr-PBA 网络的显著变化与 Hofmann 类似自旋交叉网络的自旋态相关。