π-Conjugated trinuclear group-9 metalladithiolenes with a triphenylene backbone.
π-Conjugated trinuclear group-9 metalladithiolenes with a triphenylene backbone.
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DOI：
10.1021/ic400110z
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发表时间：
2013-06
影响因子：
4.6
通讯作者：
R. Sakamoto;Tetsuya Kambe;Satoru Tsukada;K. Takada;K. Hoshiko;Y. Kitagawa;M. Okumura;H. Nishihara
中科院分区：
文献类型：
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作者：
R. Sakamoto;Tetsuya Kambe;Satoru Tsukada;K. Takada;K. Hoshiko;Y. Kitagawa;M. Okumura;H. Nishihara
在此之前，我们合成了基于苯己硫醇的π共轭三核金属硫烯配合物(J.道尔顿译，1998,2651；道尔顿译，2009,1939；Inorg。Chem.2011，50,6856)。在这里，我们报道了具有三苯主链的三核配合物。在三乙胺存在下与三苯基己硫醇和第9族金属前体反应生成三核配合物9-11。用单晶X-射线衍射法确定了11的平面结构。与单核12-14相比，9-11的配体-金属电荷转移带向更长的波长移动。电化学测试表明，单电子和双电子还原的混价态在热力学上是稳定的。9个还原物种的UV-VIS-NIR光谱确定了9(-)和9(2-)的价间电荷转移带，证实了三个金属核之间存在电子通讯。这些观察结果证明，三苯主链在三个金属硫烯单元之间传递π-共轭。
Previously, we synthesized π-conjugated trinuclear metalladithiolene complexes based on benzenehexathiol (J. Chem. Soc., Dalton Trans.1998, 2651; Dalton Trans.2009, 1939; Inorg. Chem.2011, 50, 6856). Here we report trinuclear complexes with a triphenylene backbone. A reaction with triphenylenehexathiol and group 9 metal precursors in the presence of triethylamine gives rise to trinuclear complexes 9-11. The planar structure of 11 is determined using single crystal X-ray diffraction analysis. The ligand-to-metal charge transfer bands of 9-11 move to longer wavelengths compared with those of mononuclear 12-14. Electrochemical measurements disclose that the one-electron and two-electron reduced mixed-valent states are stabilized thermodynamically. UV-vis-NIR spectroscopy for the reduced species of 9 identifies intervalence charge transfer bands for 9(-) and 9(2-), substantiating the existence of electronic communication among the three metal nuclei. These observations prove that the triphenylene backbone transmits π-conjugation among the three metalladithiolene units.