Carbonyl Amine/Schiff Base Ligands in Manganese Complexes: Theoretical Study on the Mechanism, Capability of NO Release

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• 作者：Weili Zheng ; Shuixing Wu ; Shanshan Zhao ; Yun Geng ; Junling Jin ; Zhongmin Su ; Qiang Fu
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：April 2, 2012
• 年：2012
• 卷：51
• 期：7
• 页码：3972-3980
• 全文大小：391K
• 年卷期：v.51,no.7(April 2, 2012)
• ISSN：1520-510X

文摘

A compound having the capability of releasing NO upon exposure to visible or near-infrared (vis or NIR) light could be a potential candidate for photodynamic therapy (PDT), which is significant for humans. Here, we investigated a series of Mn(II) complexes (a鈥?b>d) based on density functional theory (DFT) to illuminate the mechanism of their behavior of releasing NO. Their structural, spectroscopic, and photodissociable properties were calculated by quantum theoretical methods to give a detailed and warranted explanation of the performance of releasing NO. The results indicate that, for a鈥?b>d, releasing NO was attributed to the electron transfer from d_yz/d_xz(Mn) orbitals to 蟺*(NO) orbitals at the second excited triplet state (T₂). Importantly, we confirmed the finding in the experiment that d could release NO upon exposure to the NIR region and, thus, may be a best candidate for PDT in a鈥?b>d. Therefore, to take d for example, the analyses of the potential energy curves (PECs) of difference states and electron density difference between the T₂ and the ground state (S₀) were performed to further provide evidence of ligand dissociation and release of NO at the T₂ state. Finally, we hope that our discussion can provide assistance to understand the behavior of the release of NO and design novel photodissociable transition metal nitrosyls for PDT applications.