Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mossbauer spectra
Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mossbauer spectra
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类霍夫曼配位聚合物 Fe(py)2[Pd(CN)4] 的自旋交叉行为与 57Fe 穆斯堡尔谱
DOI：
10.1007/s10751-017-1436-4
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发表时间：
2017
影响因子：
--
通讯作者：
Takahashi Masashi
中科院分区：
文献类型：
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作者：
Kitazawa Takafumi;Kishida Takanori;Kawasaki Takeshi;Takahashi Masashi
我们制备了二维自旋交叉配合物Fe(L)2Pd(CN)4（L = py:1a； py- d5:1波段py- 15n:1c）。通过57fe穆斯堡尔光谱测量、单晶x射线测定和SQUID测量对其进行了表征。1的Mössbauer谱图表明，铁（II）自旋态在298 K时处于高自旋态，在77 K时处于低自旋态。在298k和90k时，晶体结构也分别表现出高自旋态和低自旋态，这与Fe(II)-N距离有关。Pd（II）离子比Ni（II）离子更大、更重，其自旋转变温度范围高于Fe(py)2Ni(CN)4。SQUID数据表明，在转变温度的很小的变化中，可能由于较大和较重的Pd（II）离子而观察到1a，1band1care之间的同位素效应。这种微妙的变化可能与围绕铁（II）原子和电子因子的不同振动之间的微妙平衡有关。
We have prepared the 2D spin crossover complexes Fe(L)2Pd(CN)4(L = py :1a; py-D5 :1band py-15N :1c).1ahas been characterised by57Fe Mossbauer spectroscopic measurements, single crystal X-ray determination and SQUID measurements. The Mössbauer spectra for1aindicate that the iron(II) spin states are in high spin states at 298 K and are in low spin states at 77 K. The crystal structures of1aat 298 K and 90 K also show the high spin state and the low spin state respectively, associated with the Fe(II)-N distances. The spin transition temperature range of1ais higher than that of Fe(py)2Ni(CN)4since Pd(II) ions are larger and heavier than Ni(II) ions. SQUID data indicate isotope effects among1a,1band1care observed in very small shifts of the transition temperatures probably due to larger and heavier Pd(II) ions. The delicate shifts would be associated with subtle balances between different vibrations around Fe(II) atoms and electronic factors.