Progress of Multi Functional Properties of Organic-Inorganic Hybrid System, A[FeIIFeIIIX3] (A = (n-CnH2n+1)4N, Spiropyran; X = C2O2S2, C2OS3, C2O3S)
Progress of Multi Functional Properties of Organic-Inorganic Hybrid System, A[FeIIFeIIIX3] (A = (n-CnH2n+1)4N, Spiropyran; X = C2O2S2, C2OS3, C2O3S)
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DOI：
10.3390/ma3053141
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发表时间：
2010-05-11
期刊：
影响因子：
3.4
通讯作者：
Kagesawa K
中科院分区：
文献类型：
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作者：
Kojima N;Enomoto M;Kida N;Kagesawa K
在自旋态位于自旋交叉区的混合价体系中，预计会出现与自旋和电荷耦合的新型共轭现象。从这个角度出发，我们研究了有机-无机杂化体系A[FeIIFeIIIX 3]（A =（n-CnH 2n +1）4 N，spiropyran; X = dto（C2 O2 S2），tto（C2 OS3），mto（C2 O3 S））的多功能性质. A[FeIIFeIII（dto）3]和A[FeIIFeIII（tto）3]经历铁磁相变，而A[FeIIFeIII（mto）3]经历亚铁磁相变。在（n-CnH 2n +1）4 N [FeIIFeIII（dto）3]（n = 3，4）中，在120 K附近发生了一种称为电荷转移相变（CTPT）的新型相变，其中Fe II和Fe III之间的热诱导电荷转移可逆地发生。在CTPT，铁的价态动态波动的频率约为0.1 MHz，这是通过确认的μ子自旋弛豫。（n-CnH 2n +1）4 N [FeIIFeIII（dto）3]的电荷转移相变和铁磁相变与插层阳离子的尺寸密切相关。在（SP）[FeIIFeIII（dto）3]（SP =螺吡喃）的情况下，SP在紫外光照射下的光致异构化诱导了[FeIIFeIII（dto）3]层的电荷转移相变和铁磁转变温度的显著变化。的情况下（n-CnH2n+1）4N[FeIIFeIII（mto）3]（mto = C2 O3 S），在FeIIIO 3S 3位的高自旋态（S = 5/2）和低自旋态（S = 1/2）之间的快速自旋平衡在宽的温度范围内发生，通过低自旋态（S = 1/2）和低自旋态（S = 1/2）之间的铁磁耦合，的FeIIIS 3 O3网站和高自旋态（S = 2）的FeIIO 6网站。
In the case of mixed-valence systems whose spin states are situated in the spin crossover region, new types of conjugated phenomena coupled with spin and charge are expected. From this viewpoint, we have investigated the multifunctional properties coupled with spin, charge and photon for the organic-inorganic hybrid system, A[FeIIFeIIIX3](A = (n-CnH2n+1)4N, spiropyran; X = dto(C2O2S2), tto(C2OS3), mto(C2O3S)). A[FeIIFeIII(dto)3] and A[FeIIFeIII(tto)3] undergo the ferromagnetic phase transitions, while A[FeIIFeIII(mto)3] undergoes a ferrimagnetic transition. In (n-CnH2n+1)4N [FeIIFeIII(dto)3](n = 3,4), a new type of phase transition called charge transfer phase transition (CTPT) takes place around 120 K, where the thermally induced charge transfer between FeII and FeIII occurs reversibly. At the CTPT, the iron valence state dynamically fluctuated with a frequency of about 0.1 MHz, which was confirmed by means of muon spin relaxation. The charge transfer phase transition and the ferromagnetic transition for (n-CnH2n+1)4N[FeIIFeIII(dto)3] remarkably depend on the size of intercalated cation. In the case of (SP)[FeIIFeIII(dto)3](SP = spiropyran), the photoinduced isomerization of SP under UV irradiation induces the charge transfer phase transition in the [FeIIFeIII(dto)3] layer and the remarkable change of the ferromagnetic transition temperature. In the case of (n-CnH2n+1)4N[FeIIFeIII(mto)3](mto = C2O3S), a rapid spin equilibrium between the high-spin state (S = 5/2) and the low-spin state (S = 1/2) at the FeIIIO3S3 site takes place in a wide temperature range, which induces the valence fluctuation of the FeS3O3 and FeO6 sites through the ferromagnetic coupling between the low spin state (S = 1/2) of the FeIIIS3O3 site and the high spin state (S = 2) of the FeIIO6 site.