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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electrochemical Behavior of meso-Substituted Porphyrins: The Role of Cation Radicals to the Half-Wave Oxidation Potential Splitting
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Electrochemical Behavior of meso-Substituted Porphyrins: The Role of Cation Radicals to the Half-Wave Oxidation Potential Splitting

机译：介孔取代的卟啉的电化学行为：阳离子自由基对半波氧化电位分裂的作用

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摘要

In this study, the electrochemical behavior of free base and zinc mesa-substituted porphyrins is examined by cyclic voltammetry (CV) and density functional theory (DFT). The results show that the half-wave oxidation potential splitting of the two oxidation states (Delta E= second E-1/2 - first E-1/2) of tetraphenylporphyrin (H2TPP) and its zinc complex (ZnTPP) are higher than those of porphyrins and their zinc complexes with meso-substituted five-membered heterocylic rings. The Delta E values follow the trend of TPP > T(3'-thienyl)P > T(3'-furyl)P > T(2'-thienyl)P for both meso-porphyrins and their respective zinc complexes. By employing DFT calculations, we have found that the trend of Delta E values is consistent with that of highest spin density (HSD) distribution and HOMO-LUMO energy gaps of cationic radicals as well as the pi-conjugation between central porphyrin and meso-substituted rings. Also, they exhibit the better resonance between the porphyrin ring with meso-substituted rings as moving from porphyrins and their zinc complexes with phenyl rings to five membered heterocyclic rings. A good agreement between calculated and experimental results indicates that cationic radicals, especially their spin density distribution, do play an important role in half-wave oxidation potential splitting of meso-porphyrins and their zinc complexes.
机译：在这项研究中，通过循环伏安法（CV）和密度泛函理论（DFT）检查了游离碱和锌台面取代的卟啉的电化学行为。结果表明，四苯基卟啉（H2TPP）及其锌配合物（ZnTPP）的两个氧化态（ΔE=第二E-1 / 2-第一E-1 / 2）的半波氧化电位分裂均高于卟啉及其锌配合物与内消旋五元杂环的键合对于中卟啉及其各自的锌配合物，ΔE值遵循TPP> T（3'-噻吩基）P> T（3'-呋喃基）P> T（2'-噻吩基）P的趋势。通过DFT计算，我们发现Delta E值的趋势与阳离子基团的最高自旋密度（HSD）分布和HOMO-LUMO能隙以及中心卟啉和内消旋取代基的pi共轭相一致。戒指。而且，当它们从卟啉及其与苯环的锌络合物转移到五元杂环时，它们在具有内消旋环的卟啉环之间表现出更好的共振。计算结果与实验结果之间的良好一致性表明，阳离子自由基，尤其是其自旋密度分布，确实在中卟啉及其锌配合物的半波氧化电位分裂中起重要作用。

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