Structural, redox, and photophysical studies of the tetra(pyridyl)porphyrin complex containing four (2,2'-bipyridine)(2,2':6',2"-terpyridine)ruthenium(II) groups.
Structural, redox, and photophysical studies of the tetra(pyridyl)porphyrin complex containing four (2,2'-bipyridine)(2,2':6',2"-terpyridine)ruthenium(II) groups.
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DOI：
10.1021/ic0602852
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发表时间：
2006-07
影响因子：
4.6
通讯作者：
Hiroki Kon;K. Tsuge;T. Imamura;Y. Sasaki;S. Ishizaka;N. Kitamura
中科院分区：
文献类型：
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作者：
Hiroki Kon;K. Tsuge;T. Imamura;Y. Sasaki;S. Ishizaka;N. Kitamura
通过吡啶氮与钌中心的配位反应，合成了多吡啶钌和吡啶卟啉的新型杂化配合物。用X射线单晶衍射法对一个1：4杂化配合物[{Ru（bpy）（trpy）}4（mu 4-H2 Py 4P）]8+（[1]8+）（bpy = 2，2 '-联吡啶; trpy = 2，2'：6 '，2”-三联吡啶; H2 Py 4P = 5，10，15，20-四（4-吡啶基）卟啉）进行了结构表征。合成了1：1的配合物[{Ru（bpy）（trpy）}（H2 PyT 3 P）]2+（[2]2+）（H2 PyT 3 P = 5-（4-吡啶基）三甲苯基卟啉）。卟啉环的Soret带向更长的波长移动并有一定的增宽，对于[1]8+，移动的程度更大。两个配合物的循环伏安图显示简单的重叠的组成氧化还原波。配合物在室温下发射微弱，在较低温度下发射变得更强。当[1]8+在>140 K和[2]2+在77-280 K时仅显示卟啉荧光时，[1]8+在<140 K时除了卟啉荧光之外还显示钌和卟啉磷光。
New hybrid complexes of polypyridyl ruthenium and pyridylporphyrins have been prepared by the coordination of pyridyl nitrogens to the ruthenium centers. A 1:4 hybrid complex, [{Ru(bpy)(trpy)}4(mu4-H2Py4P)]8+ ([1]8+) (bpy = 2,2'-bipyridine; trpy = 2,2':6',2"-terpyridine; H2Py4P = 5,10,15,20-tetra(4-pyridyl)porphyrin), has been characterized by the single-crystal X-ray diffraction method. A 1:1 complex, [{Ru(bpy)(trpy)}(H2PyT3P)]2+ ([2]2+) (H2PyT3P = 5-(4-pyridyl)tritolylporphyrin) has also been prepared. The Soret band of the porphyrin ring shifts to longer wavelength with some broadening, the extent of the shift being larger for [1]8+. Cyclic voltammograms of the two complexes show simple overlap of the component redox waves. The complexes are weakly emissive at room temperature, which becomes stronger at lower temperatures. While [1]8+ at >140 K and [2]2+ at 77-280 K show only porphyrin fluorescence, [1]8+ at <140 K shows ruthenium and porphyrin phosphorescence, in addition to the porphyrin fluorescence.