4.7 Article

Highly Oxidized Cobalt Porphyrin Dimer: Control of Spin Coupling via a Bridge

期刊

INORGANIC CHEMISTRY
卷 61, 期 22, 页码 8419-8430

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03807

关键词

-

资金

  1. Science and Engineering Research Board (SERB-STAR), New Delhi, India
  2. Council of Scientific and Industrial Research (CSIR), New Delhi
  3. Department of Science and Technology, India
  4. Council of Scientific and Industrial Research (CSIR)
  5. DST
  6. Regione Autonoma della Sardegna [RASSR79857]
  7. Fondazione di Sardegna [FdSGarribba2017]

向作者/读者索取更多资源

This study reveals the crucial role of the nature of the bridge in long-range electronic communication through the construction of a cobalt porphyrin dimer.
A cobalt porphyrin dimer is constructed in which two Co(II)porphyrins are connected covalently through a redox-active diethylpyrrole moiety via a flexible but nonconjugated methylene bridge. Upon oxidation with even a mild oxidant such as iodine, each cobalt(II) center and A r porphyrin ring undergo 1e(-) oxidation, leading to the formation of a 4e(-). oxidized cobalt(III)porphyrin dication diradical complex. Other oxidants such as Cl-2 and Br-2 also produce similar results. To stabilize such highly oxidized dication diradicals, the nonconjugated methylene spacer undergoes a facile and spontaneous oxidation to form a methine group with a drastic structural change, thereby making the bridge fully pi-conjugated and enabling through-bond communication. This results in a strong spin coupling between two pi-cation radicals which stabilizes the singlet state. The experimental observations are also strongly supported by extensive density functional theory calculations. The present study highlights the crucial role played by the nature of the bridge in the long-range electronic communication.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.7
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据