Tuning of redox potentials by introducing a cyclometalated bond to bis-tridentate ruthenium(II) complexes bearing bis(N-methylbenzimidazolyl)benzene or -pyridine ligands.
Tuning of redox potentials by introducing a cyclometalated bond to bis-tridentate ruthenium(II) complexes bearing bis(N-methylbenzimidazolyl)benzene or -pyridine ligands.
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DOI：
10.1021/ic2016885
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发表时间：
2012-01
影响因子：
4.6
通讯作者：
Wen-Wen Yang-Wen;Yu‐Wu Zhong;S. Yoshikawa;Jiang‐Yang Shao;Shigeyuki Masaoka;K. Sakai;J. Yao;Masa-aki Haga
中科院分区：
文献类型：
--
作者：
Wen-Wen Yang-Wen;Yu‐Wu Zhong;S. Yoshikawa;Jiang‐Yang Shao;Shigeyuki Masaoka;K. Sakai;J. Yao;Masa-aki Haga
合成并表征了一系列不对称的双三齿环化配合物[Ru（Mebib）（Mebip）]（+）、[Ru（Mebip）（dpb）]（+）、[Ru（Mebip）（Medpb）]（+）和[Ru（Mebib）（tpy）]（+）以及两个双三齿非环化配合物[Ru（Mebip）（2）]（2+）和[Ru（Mebip）（tpy）]（2+），其中Mebib是双三齿的，在一些实施方案中，R1是2-（N-甲基苯并咪唑基）苯，Mebip是双（N-甲基苯并咪唑基）吡啶，dpb是1，3-二-2-吡啶基苯，Medpb是4，6-二甲基-1，3-二-2-吡啶基苯，并且tpy是2，2 '：6'，2“-三联吡啶。用X射线晶体学方法研究了[Ru（Mebip）（Medpb）]（+）的固态结构。研究了这些钌配合物的电化学和光谱性质，并与已知配合物[Ru（tpy）（dpb）]（+）和[Ru（tpy）（2）]（2+）进行了比较。支持配体和配位环境的变化允许逐步调制的金属相关的氧化还原电位（Ru（II/III））从+0.26至+1.32 V对Ag/AgCl。在这些配合物中引入钌环化键导致显着的负电位偏移。根据Lever的电化学参数（E（L））分析了这些配合物的Ru（II/III）电位。采用密度泛函理论（DFT）和含时密度泛函理论（TDFT）研究了Mebib和Mebip配合物的电子结构和光谱性质。
A series of asymmetrical bis-tridentate cyclometalated complexes including [Ru(Mebib)(Mebip)](+), [Ru(Mebip)(dpb)](+), [Ru(Mebip)(Medpb)](+), and [Ru(Mebib)(tpy)](+) and two bis-tridentate noncyclometalated complexes [Ru(Mebip)(2)](2+) and [Ru(Mebip)(tpy)](2+) were prepared and characterized, where Mebib is bis(N-methylbenzimidazolyl)benzene, Mebip is bis(N-methylbenzimidazolyl)pyridine, dpb is 1,3-di-2-pyridylbenzene, Medpb is 4,6-dimethyl-1,3-di-2-pyridylbenzene, and tpy is 2,2':6',2″-terpyridine. The solid-state structure of [Ru(Mebip)(Medpb)](+) is studied by X-ray crystallographic analysis. The electrochemical and spectroscopic properties of these ruthenium complexes were studied and compared with those of known complexes [Ru(tpy)(dpb)](+) and [Ru(tpy)(2)](2+). The change of the supporting ligands and coordination environment allows progressive modulation of the metal-associated redox potentials (Ru(II/III)) from +0.26 to +1.32 V vs Ag/AgCl. The introduction of a ruthenium cyclometalated bond in these complexes results in a significant negative potential shift. The Ru(II/III) potentials of these complexes were analyzed on the basis of Lever's electrochemical parameters (E(L)). Density functional theory (DFT) and time-dependent DFT calculations were carried out to elucidate the electronic structures and spectroscopic spectra of complexes with Mebib or Mebip ligands.