[ruthenium(II)(cis-bis(4,4'-dicarboxylic acid 2,2'-bipyridyl))(thiocyanate)(isothiocyanate)] | 178555-81-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [ruthenium(II)(cis-bis(4,4'-dicarboxylic acid 2,2'-bipyridyl))(thiocyanate)(isothiocyanate)]
• CAS: 178555-81-2
• 化学式: C₂₆H₁₆N₆O₈RuS₂
• 分子量: 705.65
• InChiKey: LOGNGZSHQGBFRQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  43
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  259
• 氢给体数：
  4
• 氢受体数：
  16

反应信息

• 作为产物：
  描述：

  (Ru(ⁱBu₂dcbpy)₂(NCS)(SCN)) 在 四丁基氢氧化铵 作用下， 以 乙腈 为溶剂， 反应 0.67h， 生成 [ruthenium(II)(cis-bis(4,4'-dicarboxylic acid 2,2'-bipyridyl))(thiocyanate)(isothiocyanate)]
  参考文献：
  名称：

  钌染料异丁酯形式的硫氰酸酯键异构现象，称为 N3

  摘要：

  使用最近报道的双（异硫氰酸根合）钌染料（N3）的异丁酯形式的方便合成的改进，我们报告了次要异构体的分离和光谱表征，其中一个 NCS− 是 N 结合的，另一个是S 界。该合成涉及 Ru(iBu2dcbpy)2Cl2 的反应，其中 iBu2dcbpy 是 4,4'-二羧基-2,2'-联吡啶的二异丁酯，具有硫氰酸盐来源。介绍了异氰酸盐、溶剂和温度对连接异构体产率的影响。除了两个连接异构体 1 和 2，部分取代的氯异硫氰酸根络合物 3，Ru(iBu2dcbpy)2Cl(NCS)，也被分离出来。使用三氟甲磺酸银选择性去除氯化物提供了获得 [Ru(iBu2dcbpy)2(吡啶)(NCS)]OTf, 4 的高产率途径。通过 1H 和 13C NMR、IR、电子吸收光谱和质谱对配合物进行表征。在 DMSO-d6 中，在 80 °C 下，2 到 1 的异构化完成并表现出一级动力学，速率常数为 0.00014

  DOI：

  10.1080/00958972.2013.879984

文献信息

• Ruthenium(II) Charge-Transfer Sensitizers Containing 4,4‘-Dicarboxy-2,2‘-bipyridine. Synthesis, Properties, and Bonding Mode of Coordinated Thio- and Selenocyanates
  作者：Oliver Kohle、Stefan Ruile、Michael Grätzel

  DOI：10.1021/ic9515665

  日期：1996.1.1

  The synthesis and properties of several complexes of Ru(II) containing 4,4'-dicarboxy-2,2'-bipyridine (dcbpyH(2)), 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (bmipy), or 2,6-bis(1-methylbenzimidazol-2-yl)-4-phenylpyridine (ph-bmipy), and monodentate ligands (X(-) = Cl-, I-, NCS-, NCSe-, CN-) are reported. The introduction of the ambident ligands X(-) = NCS-, NCSe-, and CN- into the coordination sphere of [Ru(bmipy)(dcbpy)I](-) and cis-Ru(dcbpyH(2))(2)Cl-2 has been studied in situ via H-1 and C-13 NMR spectroscopy using C-13-enriched ligands X(-). Introduction of thiocyanate and selenocyanate initially yields the two possible linkage isomers in comparable amounts; prolonged reaction time converts the S-bound isomer and the Se-bound isomer to the N-bound isomers. The isoselenocyanate complex decomposes rapidly, yielding the cyano complex under loss of Se. The N-bound isothiocyanato complex K[Ru(bmipy)(dcbpy)(NCS)] was found to be an efficient sensitizer for nanocrystalline TiO2; the incident monochromatic photon-to-current efficiency (IPCE) is nearly quantitative at 520 nm. Introduction of a phenyl group in the 4-position of the 2,6-bis(1-methylbenzimidazol-2-yl)pyridine ligand gives a red-shifted absorption maximum for the corresponding phenylated K[Ru(ph-bmipy)(dcbpy)(NCS)] complex with an increased molar absorption coefficient for the MLCT maximum at 508 nm. At longer wavelengths above 620 nm, phenyl substitution does not enhance the absorption coefficients of the complex. Compared to that of K[Ru(bmipy)(dcbpy)(NCS)], the performance of the phenylated complex is reduced in a solar cell due to lower IPCE values. The visible spectra of the halide complexes K[Ru(bmipy)(dcbpy)X] (X(-) = Cl-, I-) show enhanced red response, but the complexes exhibit strongly reduced overall IPCE values. A comparison of the complexes to cis-Ru(dcbpyH(2))(2)(NCS)(2) is presented. Possible strategies for the design of more efficient sensitizers are discussed.