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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Synthesis and physical properties of ruthenium bipyridine complexes with TCNQ and TCNE ligands
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Synthesis and physical properties of ruthenium bipyridine complexes with TCNQ and TCNE ligands

机译：具有TCNQ和TCNE配体的钌联吡啶配合物的合成和物理性质

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摘要

[Ru(bpy)(dcbH(2))(TCNQ)Cl] center dot (Ru-TCNQ) and [Ru(bpy)(dcbH(2))(TCNE)Cl] center dot (Ru-TCNE) complexes, where bpy = 2,2'-bipyridine, dcbH(2) = 4,4'-dicarboxy-2,2'-bipyridine. TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, and TCNE = tetracyanoethylene, were synthesized and characterized by spectroscopic and electrochemical techniques. Comparatively to the TCNX ligands (TCNQ and TCNE) free of coordination, the infrared vibrational spectra of the complexes indicate that the coordination to the ruthenium atom occurs through only one nitrile group. Also, the downshift of these bands is indicative of the TCNX reduced form (TCNX center dot-). This conclusion is reinforced by EPR spectra with g = 2.005 and 2.010 for the Ru-TCNQ and Ru-TCNE complexes, respectively. In addition, the structured absorption spectra observed for both complexes indicate that the TCNX moieties are coordinated as anion radicals, (TCNX center dot-). Preliminaries luminescence studies indicate that the Ru-TCNX complexes present emission properties with reasonable lifetimes. The degree of charge transfer for the Ru-TCNQ and Ru-TCNE compounds was evaluated as 0.66 and 0.78, respectively. The Ru-III/II redox potentials (E-ox) for the Ru-TCNQ and Ru-TCNE complexes are observed, respectively, at 0.70 V and 1.30 V versus NHE. The data, all together, suggest that the TCNE species presents a higher charge uptake capability than TCNQ ligand.
机译：[Ru（bpy）（dcbH（2））（TCNQ）Cl]中心点（Ru-TCNQ）和[Ru（bpy）（dcbH（2））（TCNE）Cl]中心点（Ru-TCNE）络合物，其中bpy = 2,2'-联吡啶，dcbH（2）= 4,4'-二羧基-2,2'-联吡啶。通过光谱和电化学技术合成并表征了TCNQ = 7,7,8,8-四氰基-对-喹二甲烷，TCNE =四氰基乙烯。与无配位的TCNX配体（TCNQ和TCNE）相比，配合物的红外振动光谱表明与钌原子的配位仅通过一个腈基发生。同样，这些频段的降档表示TCNX格式减小（TCNX中心点）。 Ru-TCNQ和Ru-TCNE配合物的ePR谱分别为g = 2.005和2.010，这一结论得到了加强。另外，观察到的两种配合物的结构化吸收光谱表明，TCNX部分被配成阴离子自由基（TCNX中心点）。初步的发光研究表明，Ru-TCNX配合物具有合理的寿命，具有发射特性。 Ru-TCNQ和Ru-TCNE化合物的电荷转移程度分别为0.66和0.78。相对于NHE，分别在0.70 V和1.30 V时观察到Ru-TCNQ和Ru-TCNE络合物的Ru-III / II氧化还原电位（E-ox）。数据一起表明，TCNE物种比TCNQ配体具有更高的电荷吸收能力。

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