Ruthenium complexes with asymmetric hydroxy- and methoxy-substituted bipyridine ligands
Ruthenium complexes with asymmetric hydroxy- and methoxy-substituted bipyridine ligands
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具有不对称羟基和甲氧基取代的联吡啶配体的钌配合物
DOI：
10.1016/j.poly.2021.115300
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发表时间：
2021
期刊：
影响因子：
2.6
通讯作者：
Paul, Jared J.
中科院分区：
文献类型：
--
作者：
Benson, Kaitlyn R.;Stash, Jaqueline;Moffa, Katherine L.;Schmehl, Russell H.;Dudley, Timothy J.;Paul, Jared J.
具有能够质子转移的配体的金属络合物的开发可以导致质子耦合电子转移（PCET）化学的显著进步，特别是理解这些反应在激发态下如何机械地发生。合成了三种含不对称联吡啶配体的钌配合物：[Ru（bpy）2（4 bpyOH）]2+、[Ru（bpy）2（4 bpyOMe）]2+和[Ru（bpy）2（44′bpy（OH）（OMe））]2+（bpy = 2，2 ′-联吡啶; 4 bpyOH = 4-羟基-2，2 ′-联吡啶; 4 bpyOMe = 4-甲氧基-2，2 ′-联吡啶; 44′bpy（OH）（OMe）= 4-羟基-4 ′-甲氧基-2，2 ′-联吡啶。这些复合物进行了研究，使用实验和计算方法。这些研究表明，甲氧基取代提供了与羟基取代相似的供电子性质，这意味着当在不存在质子转移的情况下检查电子转移时，甲氧基取代是良好的对照。电位-pH图表明，[Ru（bpy）2（4 bpyOH）]2+在酸性水溶液中的RuIII/II还原电位为0.97 V（vs. Ag/AgCl），去质子化后降至0.76 V（vs. Ag/AgCl）。[Ru（bpy）2（44′bpy（OH）（OMe））]2+在酸性水溶液中的还原电位为0.92 V（vs. Ag/AgCl），在去质子化后的还原电位为0.74 V（vs. Ag/AgCl）。这些配合物是可比的其他羟基和甲氧基取代的多吡啶基钌配合物先前报道，显示添加剂的影响，羟基和甲氧基取代的还原电位的RuIII/II波和光谱的变化，发生作为配体骨架被改变。
The development of metal complexes with ligands capable of proton transfer can result in significant advances in Proton Coupled Electron Transfer (PCET) chemistry, specifically understanding how these reactions occur mechanistically in the excited state. The synthesis of three ruthenium complexes containing asymmetric bipyridine ligands: [Ru(bpy)2(4bpyOH)]2+, [Ru(bpy)2(4bpyOMe)]2+, and [Ru(bpy)2(44′bpy(OH)(OMe))]2+(bpy = 2,2′-bipyridine; 4bpyOH = 4-hydroxy-2,2′-bipyridine; 4bpyOMe = 4-methoxy-2,2′-bipyridine; 44′bpy(OH)(OMe) = 4-hydroxy-4′-methoxy-2,2′-bipyridine) are reported. These complexes were studied using both experimental and computational methods. These studies indicate that the methoxy-substitution gives similar electron-donating properties to the hydroxy-substitution, meaning that the methoxy-substitution is a good control when examining electron transfer in the absence of proton transfer. Potential versus pH diagrams show that [Ru(bpy)2(4bpyOH)]2+has a RuIII/IIreduction potential of 0.97 V vs. Ag/AgCl in aqueous acidic solution that decreases to 0.76 V vs. Ag/AgCl when deprotonated. The [Ru(bpy)2(44′bpy(OH)(OMe))]2+, with an additional methoxy-substituent, has a RuIII/IIreduction potential that is slightly lower with a potential of 0.92 V vs. Ag/AgCl in acidic aqueous solution that decreases to 0.74 V vs. Ag/AgCl when deprotonated. These complexes are comparable to other hydroxy- and methoxy-substituted polypyridyl ruthenium complexes reported previously, showing the additive effects of hydroxy- and methoxy-substitutions on the reduction potential of the RuIII/IIwave and spectroscopic shifts that occur as the ligand scaffold is altered.
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影响因子：
12.9
作者：
Costentin, Cyrille
通讯作者：
Costentin, Cyrille
影响因子：
4.6
作者：
DAUL, C;BAERENDS, EJ;VERNOOIJS, P
通讯作者：
VERNOOIJS, P
三联吡啶 Ru(II) 敏化剂电子结构的密度泛函分析
DOI：
--
发表时间：
2010
期刊：
影响因子：
--
作者：
G. Wilson;G. Will
通讯作者：
G. Will
影响因子：
15
作者：
Young ER;Rosenthal J;Hodgkiss JM;Nocera DG
通讯作者：
Nocera DG
影响因子：
4.6
作者：
Bronner, Catherine;Wenger, Oliver S.
通讯作者：
Wenger, Oliver S.