Electrochemical and spectroelectrochemical studies of β-phosphorylated Zn porphyrins
Electrochemical and spectroelectrochemical studies of β-phosphorylated Zn porphyrins
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β-磷酸化锌卟啉的电化学和光谱电化学研究
DOI：
10.1142/s1088424613500958
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发表时间：
2013
影响因子：
1.5
通讯作者：
R. Guilard
中科院分区：
文献类型：
--
作者：
Yuanyuan Fang;K. Kadish;Ping Chen;Yulia G. Gorbunova;Y. Y. Enakieva;A. Tsivadze;A. Bessmertnykh;R. Guilard
研究了两种β-磷酸化锌卟啉化合物[2-二乙氧基磷酰基-5，10，15，20-四苯基卟啉]锌（1）和[2-二异丙氧基磷酰基-5，10，15，20-四苯基卟啉]锌（2）在四丁基高氯酸铵（TBAP）或四丁基六氟磷酸铵（TBAPF 6）支持电解质存在下的电化学和光谱电化学性质.在某些溶液条件下，观察到三个单电子还原，最后一个过程归因于形成卟啉二价阴离子后的化学反应产物。对于相同的化合物，观察到两个或三个氧化，同样取决于溶液条件。在某些情况下，观察到两个明确定义和良好分离的单电子氧化，但在其他情况下，第一个单电子提取得到卟啉自由基阳离子被分成两个氧化还原过程，彼此分离110-140 mV。这种分裂的第一氧化成两个过程是由于连接的两个卟啉，这导致当一个P=O单元的磷酰基取代基上的一个卟啉结合到第二卟啉的Zn（II）中心，导致二聚体的形成。根据两个分裂氧化还原过程之间的电位差（ΔE1/2）讨论了两个大环之间的相互作用，并将总体数据与文献中报道的其他卟啉二聚体和双大环进行了比较。
The electrochemical and spectroelectrochemical properties of two β-phosphorylated Zn porphyrins, [2-diethoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (1) and [2-diisopropoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (2), are reported in CH2Cl2 and PhCN containing tetrabutylammonium perchlorate (TBAP) or tetrabutylammonium hexafluorophosphate (TBAPF6) as supporting electrolyte. Under certain solution conditions, three one-electron reductions are observed, with the last process being attributed to the product of a chemical reaction following formation of the porphyrin dianion. Two or three oxidations are observed for the same compounds, again depending upon the solution conditions. In some cases, two well-defined and well-separated one electron oxidations are observed but in others the first one-electron abstraction to give the porphyrin radical cation is split into two redox processes, separated from each other by 110–140 mV. This splitting of the first oxidation into two processes is attributed to linking of the two porphyrins which results when a P=O unit of the phosphoryl substituent on one porphyrin binds to the Zn(II) center of a second porphyrin, resulting in dimer formation. The interaction between the two macrocycles is discussed in terms of the difference in potentials between the two split redox processes (ΔE1/2) and the overall data is compared with that for other porphyrin dimers and bis-macrocycles reported in the literature.
影响因子：
4.6
作者：
Chen, Ping;Finikova, Olga S.;Kadish, Karl M.
通讯作者：
Kadish, Karl M.