Structure, Spectroscopy, and Reactivity Properties of Porphyrin Pincers: A Conceptual Density Functional Theory and Time-Dependent Density Functional Theory Study

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• 作者：Ying Huang ; Aiguo Zhong ; Chunying Rong ; Xiaoming Xiao ; Shubin Liu
• 刊名：Journal of Physical Chemistry A
• 出版年：2008
• 出版时间：January 17, 2008
• 年：2008
• 卷：112
• 期：2
• 页码：305 - 311
• 全文大小：406K
• 年卷期：v.112,no.2(January 17, 2008)
• ISSN：1520-5215

文摘

Porphyrin and pincer complexes are both important categories of compounds in biological and catalytic systems.The idea to combine them is computationally investigated in this work. By employment of density functionaltheory (DFT), conceptual DFT, and time-dependent DFT approaches, structure, spectroscopy, and reactivityproperties of porphyrin pincers are systematically studied for a selection of divalent metal ions. We foundthat the porphyrin pincers are structurally and spectroscopically different from their precursors and are morereactive in electrophilic and nucleophilic reactions. A few quantitative linear/exponential relationships havebeen discovered between bonding interactions, charge distributions, and DFT chemical reactivity indices.These results are implicative in chemical modification of hemoproteins and understanding chemical reactivityin heme-containing and other biologically important complexes and cofactors.