Synthesis and characterization of mono- and dinuclear phenanthroline-extended tetramesitylporphyrin complexes as well as UV-Vis and EPR studies on their one-electron reduced species.
Synthesis and characterization of mono- and dinuclear phenanthroline-extended tetramesitylporphyrin complexes as well as UV-Vis and EPR studies on their one-electron reduced species.
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DOI：
10.1039/c2dt32196c
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发表时间：
2013-02
影响因子：
4
通讯作者：
Corinna Matlachowski;M. Schwalbe
中科院分区：
文献类型：
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作者：
Corinna Matlachowski;M. Schwalbe
报道了基于稠合卟啉菲咯啉配体（H(2)-1）的单核化合物及其相应的双核卟啉双联吡啶钌配合物的合成。配体的扩展 π 系统能够存储电子当量，这可以通过 KC(8)（和/或 Na(Hg)）的单电子还原以及随后的 UV-Vis 和 EPR 分析来证明。在二氯甲烷-三乙胺混合物中，在光照下也可以实现电子还原。配体的两个配位球不同，因此可以根据反应条件分离单核或（异）双核配合物。我们可以成功地将 Zn、Cu 和 Pd 引入卟啉单元，产生一系列单核 (M-1) 化合物。此外，我们可以连接双-(4,4'-二叔丁基-2,2'-联吡啶)钌片段(Ru(tbbpy)(2)(2+))以获得双核(M-1-Ru)金属配合物。对于 Zn-1，可以获得 X 射线晶体结构，证实了卟啉单元中的选择性金属化。所有金属络合物均使用标准分析工具（元素分析、质谱和 NMR（或 EPR）光谱）进行分离和表征。
The syntheses of mononuclear compounds based on the fused porphyrin phenanthroline ligand (H(2)-1) and their corresponding dinuclear porphyrin bis-bipyridine ruthenium complexes are reported. The extended π-system of the ligand is able to store electron equivalents as could be proven by the single electron reduction with KC(8) (and/or Na(Hg)) followed by subsequent UV-Vis and EPR analysis. Electron reduction could also be achieved under light illumination in a dichloromethane-triethylamine mixture. The two coordination spheres of the ligand are different so that mononuclear or (hetero)dinuclear complexes can be isolated depending on the reaction conditions. We could successfully introduce Zn, Cu and Pd into the porphyrinic unit leading to a series of mononuclear (M-1) compounds. Further, we could attach the bis-(4,4'-di-tert-butyl-2,2'-bipyridine) ruthenium fragment (Ru(tbbpy)(2)(2+)) to obtain dinuclear (M-1-Ru) metal complexes. In the case of Zn-1 an X-ray crystal structure could be obtained confirming the selective metallation in the porphyrinic unit. All metal complexes were isolated and characterized with standard analytical tools (elemental analysis, mass spectrometry and NMR (or EPR) spectroscopy).