Assistance of the Iron Porphyrin Ligands to the Binding Interaction between the Fe Center and Small Molecules in Solution

详细信息    查看全文

• 作者：Jie Xiao ; Ronny Golnak ; Kaan Atak ; Mika Pfl眉ger ; Marvin Pohl ; Edlira Suljoti ; Bernd Winter ; Emad F. Aziz
• 刊名：Journal of Physical Chemistry B
• 出版年：2014
• 出版时间：August 7, 2014
• 年：2014
• 卷：118
• 期：31
• 页码：9371-9377
• 全文大小：318K
• ISSN：1520-5207

文摘

Solute鈥搒olvent electronic structure interactions of iron porphyrin at very low concentration in dichloromethane (CH₂Cl₂) liquid solution are reported. Two iron porphyrin complexes are investigated here鈥攊ron octaethylporphyrin chloride (FeOEP-Cl) and iron tetraphenylporphyrin chloride (FeTPP-Cl)鈥攗sing X-ray absorption and emission spectroscopy at the Fe L_2,3 edge, and spectra are interpreted with the help of density functional theory/restricted open-shell configuration interaction singles (DFT/ROCIS) calculations. It is argued that the Fe center of FeOEP-Cl is more capable of binding small solvent molecules, exemplified here for Cl₂CH₂, than FeTPP-Cl in solution. The proposed binding mechanism is through the assistance of the dipole interaction between the porphyrin鈥搇igand system and the solvent molecule, in a situation where the ligand structure and arrangement maximize the binding interactions. Our studies demonstrate that even small ligands, depending on their structure and arrangement, can have considerable effects on porphyrin鈥檚 metal center chemistry in liquid solution.