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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The redox series [Ru(bpy)_2(L)]~n, n = +3, +2, +1, 0, with L = bipyridine, “click” derived pyridyl-triazole or bis-triazole: a combined structural, electrochemical, spectroelectrochemical and DFT investigation?
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The redox series [Ru(bpy)_2(L)]~n, n = +3, +2, +1, 0, with L = bipyridine, “click” derived pyridyl-triazole or bis-triazole: a combined structural, electrochemical, spectroelectrochemical and DFT investigation?

机译：氧化还原系列[Ru（bpy）_2（L）]〜n，n = + 3，+ 2，+ 1、0，其中L =联吡啶，“点击”衍生出吡啶基三唑或双三唑：组合结构，电化学，光谱电化学和DFT研究？

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The compounds [Ru(bpy)_2(L~1)](ClO_4)_2 (1(ClO_4)_2), [Ru(bpy)_2(L~2)](ClO_4)_2 (2(ClO_4)_2), [Ru(bpy)_2(L~3)](ClO_4)_2 (3(ClO_4)_2), [Ru(bpy)_2(L~4)](ClO_4)_2 (4(ClO_4)_2), [Ru(bpy)_2(L~5)](ClO_4)_2 (5(ClO_4)_2), and [Ru(bpy)_2(L~6)](ClO_4)_2 6(ClO_4)_2 (bpy = 2,2’-bipyridine, L~1 = 1-(4-isopropyl-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L~2 = 1-(4- butoxy-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L~3 = 1-(2-trifluoromethyl-phenyl)-4-(2-pyridyl)-1,2,3-triazole, L~4 = 4,4’-bis-{1-(2,6-diisopropyl-phenyl)}-1,2,3-triazole, L~5 = 4,4’-bis-{(1-phenyl)}-1,2,3-triazole, L~6 = 4,4’-bis-{1-(2-trifluoromethyl-phenyl)}-1,2,3-triazole) were synthesized from [Ru(bpy)_2(EtOH)_2]- (ClO_4)_2 and the corresponding “click”-derived pyridyl-triazole or bis-triazole ligands, and characterized by ~1H-NMR spectroscopy, elemental analysis, mass spectrometry and X-ray crystallography. Structural analysis showed a distorted octahedral coordination environment about the Ru(II) centers, and shorter Ru–N- (triazole) bond distances compared to Ru–N(pyridine) distances in complexes of mixed-donor ligands. All the complexes were subjected to cyclic voltammetric studies, and the results were compared to the wellknown [Ru(bpy)_3]~(2+) compound. The oxidation and reduction potentials were found to be largely uninfluenced by ligand changes, with all the investigated complexes showing their oxidation and reduction steps at rather similar potentials. A combined UV-vis-NIR and EPR spectroelectrochemical investigation, together with DFT calculations, was used to determine the site of electron transfer in these complexes. These results provided insights into their electronic structures in the various investigated redox states, showed subtle differences in the spectroscopic signatures of these complexes despite their similar electrochemical properties, and provided clues to the unperturbed redox potentials in these complexes with respect to ligand substitutions. The reduced forms of the complexes display structured absorption bands in the NIR region. Additionally, we also present new synthetic routes for the ligands presented here using Cu-abnormal carbene catalysts.
机译：化合物[Ru（bpy）_2（L〜1）]（ClO_4）_2（1（ClO_4）_2），[Ru（bpy）_2（L〜2）]（ClO_4）_2（2（ClO_4）_2）， [Ru（bpy）_2（L〜3）]（ClO_4）_2（3（ClO_4）_2），[Ru（bpy）_2（L〜4）]（ClO_4）_2（4（ClO_4）_2），[Ru （bpy）_2（L〜5）]（ClO_4）_2（5（ClO_4）_2）和[Ru（bpy）_2（L〜6）]（ClO_4）_2 6（ClO_4）_2（bpy = 2,2 '-联吡啶，L〜1 = 1-（4-异丙基-苯基）-4-（2-吡啶基）-1,2,3-三唑，L〜2 = 1-（4-丁氧基-苯基）-4- （2-吡啶基）-1,2,3-三唑，L〜3 = 1-（2-三氟甲基-苯基）-4-（2-吡啶基）-1,2,3-三唑，L〜4 = 4， 4'-双-{1-（2,6-二异丙基-苯基）}-1,2,3-三唑，L〜5 = 4,4'-双-{{（1-苯基）}-1,2，由[Ru（bpy）_2（EtOH）_2]-合成L〜6 = 4,4'-双-{1-（2-三氟甲基-苯基）}-1,2,3-三唑（ClO_4）_2和相应的“点击”衍生的吡啶基三唑或双三唑配体，并通过〜1H-NMR光谱，元素分析，质谱和X射线晶体学表征。结构分析表明，在混合施主配体的配合物中，Ru（II）中心周围的八面体配位环境变形，Ru-N-（三唑）键距比Ru-N（吡啶）距短。所有的配合物都进行了循环伏安法研究，并将其结果与著名的[Ru（bpy）_3]〜（2+）化合物进行了比较。发现氧化和还原电势在很大程度上不受配体变化的影响，所有研究的络合物均以相似的电势显示其氧化和还原步骤。结合了紫外可见近红外光谱和EPR光谱电化学研究以及DFT计算，来确定这些络合物中电子的转移位置。这些结果提供了在各种研究的氧化还原状态下其电子结构的见解，显示了尽管它们具有相似的电化学性质，但这些络合物的光谱特征存在细微差异，并提供了这些络合物在配体取代方面不受干扰的氧化电位的线索。络合物的还原形式在NIR区域显示结构化的吸收带。此外，我们还提出了使用铜异常卡宾催化剂对此处呈现的配体进行合成的新途径。

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