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SYNTHESIS AND PROPERTIES OF IRON(III) PORPHYRIN COMPLEXES WITH NOVEL SPIN STATE

新型自旋态铁(III)卟啉配合物的合成及性能

基本信息

批准号：
14540521
负责人：
NAKAMURA Mikio
金额：
$ 2.18万
依托单位：
TOHO UNIVERSTIY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540521/
关键词：
PORPHYRIN IRON COMPLEXES SPIN CROSSOVER SADDLED DEFORMATION ^<13>C NMR EPR MOSSBAUER SQUID 中間スピン電子配置 ^1H NMR Massbauer

项目摘要

i)By the coordination of weak THF ligand to the iron(III) complexes with highly ruffled porphyrin ring, we were able to prepare essentially pure intermediate spin complexes. The ^<13>C NMR measurements have revealed that these complexes adopt a novel (d_<xz>, d_<yz>)^3(d_<xy>)^1(d_z^2)^1 electron configuration; the intermediate spin iron(III) complexes reported previously are believed to have (d_<xy>)^2(d_<xz>, d_<yz>)^2(d_z^2)^1 electron configuration.ii)The electron configuration of the low spin (S = 1) manganese(III) complexes with highly ruffled porphyrin ring has also been examined. In contrast to the case of the corresponding iron(III) complexes, they have shown a common (d_<xy>)^2(d_<xz>, d_<yz>)^2 electron configuration. The result suggests, that the d_π orbitals are located higher in energy than the d_<xy> orbital in the case of manganese complexes even if the porphyrin ring is highly ruffled.iii)The iron(III) complex with highly saddled porphyrin ring was treated with pyridine and substituted pyridine. The magnetic properties of the bis(pyridine) complex thus formed were examined by ^1H NMR, ^<13>C NMR, EPR, and Mossbauer spectroscopy as well as X-ray crystallography and SQUID magnetometry. While the complex showed a spin crossover between the S = 1/2 and S = 3/2 spin states in solution, the same complex maintained the S = 1/2 in the solid. The X-ray crystallographic measurements at different temperatures have revealed that the complex is tightly packed in the crystal lattice. Consequently, there is little space for the axial ligand to change the Fe-Ligand bond length. On the basis of these results, we have concluded that the enough cavity is necessary around the axial ligand for the complex to show the spin crossover process.

i)通过弱THF配体与具有高度褶皱卟啉环的铁(III)络合物的配位，我们能够制备基本上纯的中间自旋络合物。 ^ 13 C NMR测量表明这些配合物采用了新颖的(d_<xz>,d_<yz>)^3(d_<xy>)^1(d_z^2)^1电子构型；先前报道的中间自旋铁（III）络合物被认为具有（d_<xy>）^2（d_<xz>，d_<yz>）^2（d_z^2）^1电子构型。ii）还检查了具有高度褶皱卟啉环的低自旋（S = 1）锰（III）络合物的电子构型。与相应的铁 (III) 配合物的情况相反，它们显示出常见的 (d_<xy>)^2(d_<xz>, d_<yz>)^2 电子构型。结果表明，在锰配合物的情况下，d_π 轨道的能量高于 d_<xy> 轨道，即使卟啉环高度褶皱。iii)用吡啶和取代吡啶处理具有高度鞍状卟啉环的铁(III)配合物。通过 1 H NMR、 13 C NMR、EPR和穆斯堡尔光谱以及X射线晶体学和SQUID磁力测定法检查由此形成的双(吡啶)络合物的磁性。虽然该配合物在溶液中显示出 S = 1/2 和 S = 3/2 自旋态之间的自旋交叉，但同一配合物在固体中保持了 S = 1/2。不同温度下的 X 射线晶体学测量表明，该配合物紧密堆积在晶格中。因此，轴向配体几乎没有空间改变铁-配体键长。根据这些结果，我们得出结论，配合物在轴向配体周围需要足够的空腔来显示自旋交叉过程。