Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
J Am Chem Soc. 2010 Mar 24;132(11):3737-50. doi: 10.1021/ja907584x.
We report detailed studies on two S = 2 electronic states of high-spin iron(II) porphyrinates. These two states are exemplified by the five-coordinate derivatives with either neutral imidazole or anionic imidazolate as the axial ligand. The application of several physical methods all demonstrate distinctive differences between the two states. These include characteristic molecular structure differences, Mossbauer spectra, magnetic circular dichroism spectroscopy, and integer-spin EPR spectral distinctions. These distinctions are supported by DFT calculations. The two states are characterized by very different spatial properties of the doubly occupied orbital of the high-spin that are consonant with the physical properties.
我们报告了对两种高自旋铁(II)卟啉物 S = 2 电子态的详细研究。这两种态分别由中性咪唑或阴离子咪唑作为轴向配体的五配位衍生物所代表。几种物理方法的应用都证明了这两种态之间存在明显的差异。这些差异包括特征分子结构差异、穆斯堡尔光谱、磁圆二色性光谱和整数自旋 EPR 光谱区别。这些区别得到了 DFT 计算的支持。这两种态的特征是高自旋的双重占据轨道具有非常不同的空间性质，这与物理性质一致。
