Bis(cyano) Iron(III) Porphyrinates: What Is the Ground State?
Bis(cyano) Iron(III) Porphyrinates: What Is the Ground State?
复制标题
双（氰基）铁（III）卟啉酸盐：什么是基态？
DOI：
10.1021/acs.inorgchem.5b00780
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发表时间：
2015-07-06
影响因子：
4.6
通讯作者：
Scheidt WR
中科院分区：
文献类型：
--
作者：
Li J;Noll BC;Schulz CE;Scheidt WR
报道了六种新的双氰基铁卟啉衍生物的合成。阴离子卟啉配合物利用四苯基卟啉、四均三甲苯基卟啉和四甲苯基卟啉作为卟啉配体。Kryptofix-222和18-C-6的钾盐用作阳离子。这些配合物的特征在于通过X射线结构分析，固态穆斯堡尔谱，EPR光谱，无论是在冷冻的二氯甲烷溶液和微晶状态。这些数据表明，这些阴离子配合物可以以（dxz，dyz）（4）（dxy）（1）或（dxy）（2）（dxz，dyz）（3）电子构型存在，并且一些可以明显容易地相互转化。这反映了这两种状态在能量上可以非常接近。除了改变卟啉配体的影响外，固态和溶液中氰化物配体环境的微妙影响足以改变两种电子状态之间的平衡。
The synthesis of six new bis(cyano) iron(III) porphyrinate derivatives is reported. The anionic porphyrin complexes utilized tetraphenylporphyrin, tetramesitylporphyrin, and tetratolylporphyrin as the porphyrin ligand. The potassium salts of Kryptofix-222 and 18-C-6 were used as the cations. These complexes have been characterized by X-ray structure analysis, solid-state Mössbauer spectroscopy, and EPR spectroscopy, both in frozen CH2Cl2 solution and in the microcrystalline state. These data show that these anionic complexes can exist in either the (dxz,dyz)(4)(dxy)(1) or the (dxy)(2)(dxz,dyz)(3) electronic configuration and some can clearly readily interconvert. This is a reflection that these two states can be very close in energy. In addition to the effects of varying the porphyrin ligand, subtle effects of the cyanide ligand environment in the solid state and in solution are sufficient to shift the balance between the two electronic states.