Synthesis and Properties of Iron(III) and Iron(II) Porphyrinates with Novel Electron Configuration and Magnetic Characteristics

卟啉环的非平面形变使得某些特定的金属-卟啉相互作用成为可能。结果表明，非平面卟啉配合物具有平面配合物所没有的电子和磁性特征。本论文制备了一系列高形变的meso-四烷基卟啉（TRP）和八乙基四苯基卟啉（OETPP）配合物，并对其电子结构和磁性进行了研究.因此，我们可以排名的基础上的吡咯-H化学位移的弱轴向配体的场强，因为高场位移的吡咯-H直接相关的人口的中间自旋复合物。我们已经确定了各种各样的氧配体的弱点，如下所示，基于一系列平面的吡咯-H化学位移， 关于我们 4-MePyNO，3，5-Me_2PyNO&gt;PyNO&gt;4-ClPyNO&gt;DMSO&gt;DMF&gt;MeOH&gt;THF&gt; Dioxane我们还根据铁卟啉配合物的^1H和^ C化学位移证实了两种具有不同电子构型的中间自旋配合物的存在，即（d_<xy>）^2（d_<xz>，d_<yz>）^2（d_z2））^1和（d_<xz>，d_<yz>）^3（d_）<xy>^1（d_z2）^1<13>。通过在OMTPP的meso-phenyl基团的3，5-位上引入大体积基团，我们能够制备其中每个分子被认为是松散堆积的晶体。SQUID和穆斯堡尔谱的测量结果表明，这些配合物在固态下确实表现出自旋交叉现象。在五配位高鞍型配合物中，我们还发现了在极低温度下S=5/2和S=3/2之间的自旋交叉过程，即带有烷基异腈的铁卟啉配合物总是处于（d_<xz>，d_<yz>）^4（d_<xy>）^1电子构型的低自旋态。本文首次发现二氮杂卟啉的烷基异腈配合物具有（d_<xy>）^2（d_<xz>，d_<yz>）^3电子构型的低自旋态。由于烷基异氰化物配体经常被用作探针来揭示天然存在的血红素蛋白的电子结构，本结果是非常有用的，以揭示血红素蛋白的功能。少

Nonplanar deformation of porphyrin ring makes some specific metal-porphyrin interactions possible. As a result, the nonplanar porphyrin complexes could exhibit some characteristic electronic and magnetic properties that can not be observed in the corresponding planar complexes. In the present study, we have prepared a series of highly deformed meso-tetraalkylporphyrins(TRP) and octaethyltetraphenylporphyrin(OETPP) complexes and have examined the electronic structures and magnetic behaviors.The intermediate-spin(S=3/2) state of iron(III) porphyrin complexes are stabilized by the axial ligands with weak field strength. Thus, we can rank the field-strength of the weak axial ligands on the basis of the pyrrole-H chemical shifts, since the upfield shift of the pyrrole-H directly correlates with the population of the intermediate-spin complex. We have determined the weakness of a wide variety of oxygen ligands as given below on the basis of the pyrrole-H chemical shifts of a series of planar … More , ruffled, and saddled porphyrin complexes.4-MePyNO,3,5-Me_2PyNO>PyNO>4-ClPyNO>DMSO>DMF>MeOH>THF>DioxaneWe have also confirmed the presence of two types of intermediate-spin complexes with different electron configurations, (d_<xy>)^2(d_<xz>,d_<yz>)^2(d_z2))^1 and (d_<xz>,d_<yz>)^3(d_<xy>)^1(d_z2)^1, on the basis of the ^1H and ^<13>C chemical shifts of a wide variety of iron(III) porphyrin complexes.Magnetic behaviors of iron(III) porphyrin complexes could be affected by the crystal packing. By the introduction of bulky groups at the 3,5-positions of meso-phenyl groups of OMTPP, we were able to prepare the crystals where each molecule is supposed to be loosely packed. The SQUID and Mossbauer measurements have revealed that these complexes actually exhibit spin-crossover phenomena in the solid state. We have also found the unprecedented example showing the spin-crossover process between S=5/2 and S=3/2 in five-coordinate highly saddled complexes at extremely low temperature.The iron(III) porphyrinates carrying alkyl isocyanide always adopt the low-spin state with the (d_<xz>,d_<yz>)^4(d_<xy>)^1 electron configuration. In the present study, we have found for the first time that the alkyl isocyanide complexes of diazaporphyrin exhibit the low-spin state with the (d_<xy>)^2(d_<xz>,d_<yz>)^3 electron configuration. Since the alkyl isocynide ligands are frequently used as probes to reveal the electronic structures of naturally occurring heme proteins, the present results are quite useful to reveal the functions of heme proteins. Less