2,2'-bipyridine-4,4'-dicarboxylic acid bis[(3-silatranylpropyl) amide] | 1428932-75-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2,2'-bipyridine-4,4'-dicarboxylic acid bis[(3-silatranylpropyl) amide]
• 英文别名: 4,4′-diamidopropylsilatrane-2,2′-bipyridine；N-[3-(2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecan-1-yl)propyl]-2-[4-[3-(2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecan-1-yl)propylcarbamoyl]pyridin-2-yl]pyridine-4-carboxamide
• CAS: 1428932-75-5
• 化学式: C₃₀H₄₄N₆O₈Si₂
• 分子量: 672.886
• InChiKey: FLBKACSDYFSZMM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.02
• 重原子数：
  46
• 可旋转键数：
  11
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  146
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  2,2'-bipyridine-4,4'-dicarboxylic acid bis[(3-silatranylpropyl) amide] 、 rhodium(III) chloride hydrate 以 N,N-二甲基甲酰胺 为溶剂， 以40%的产率得到cis-[Ru(bipy-sil)₂Cl₂]
  参考文献：
  名称：

  Silane: A new linker for chromophores in dye-sensitised solar cells

  摘要：

  A series of ruthenium(II) polypyridyl complexes, with novel silane functionalisation, [Ru(bipy)(2)(bipy-sil)] (PF6)(2) (3), [Ru(bipy-sil)(2)Cl-2] (6), and [Ru(bipy-sil)(2)(NCS)(2)] (7) have been synthesised and tested as chromophores (dyes) in TiO2 and WO3 based dye-sensitised solar cells (DSSCs). The performance of the respective DSSCs were compared to analogous dyes with ionic carboxylate ([Ru(bipy)(2)(dcbipy)](PF6)(2) (1), [Ru(dcbipy)(2)Cl-2] (4), [Ru(dcbipy)(2)(NCS)(2)] (5)) or phosphonate ([Ru(bipy)(2)(dpipy)](PF6)(2) (2)) linking groups. The covalent silane-metal oxide linkage offers much needed improvement to the operating conditions, and lifetime of DSSCs, in terms of pH range and choice of solvent. UV-Vis spectroscopy of the deep-red solutions showed that the bis-bipy-sil complexes absorbed more visible light than the tris-bipy complex, as indicated by the presence of two absorption bands and higher E values. The UV-Vis spectrum of (3) contained a single broad absorption at 400-600 nm with: lambda(max) = 457 nm; epsilon = 10520 +/- 440 L mol(-1) cm(-1), whereas two intense broad absorption bands were observed for novel bis-bipy-sil complexes (6): 340-370 nm (lambda(max(1)) = 365 nm, epsilon((1)) = 12716 +/- 180 L mol(-1) cm(-1)); and 440-540 nm (lambda(max(2)) = 485 nm, epsilon((2)) = 11070 +/- 150 L mol(-1) cm(-1)), and (7): 340-400 nm (lambda(max) = 371 nm epsilon((1)) = 20690 +/- 485 L mol(-1) cm(-1)), and 460-530 nm (lambda(max) = 500 nm and epsilon((2)) = 20750 +/- 487 L mol(-1) cm(-1)). The bands in (7) being significantly more defined.A 10-fold improvement in the efficiency of the bipy-sil TiO2-based DSSCs was observed from (3) to (6) to (7). This performance was lower than that of the commercial N3 dye, [Ru(dcbipy)(2)(NCS)(2)] (5), but the current of (7) on WO3, was comparable to that of the carboxylate system (4). There is considerable potential for further improvement by modification of the silyl linker, reducing the long non-conjugated propyl chain between the amide group and the silatrane (bipy-sil), to a short, conjugated link. During an extensive synthetic study, the most promising strategy was identified as direct linkage, the formation of a direct Si-C bond, using butyllithium with 4,4'-dibromo-2,2'-bipyridine and either trimethylsilane or 1-ethoxysilatrane, provided that the product can be captured and stabilised prior to binding to a metal oxide coated DSSC substrate. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.07.078
• 作为产物：
  描述：

  2,2'-联吡啶-4,4'-二甲酸 在 氯化亚砜 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.0h， 生成 2,2'-bipyridine-4,4'-dicarboxylic acid bis[(3-silatranylpropyl) amide]
  参考文献：
  名称：

  Silane: A new linker for chromophores in dye-sensitised solar cells

  摘要：

  A series of ruthenium(II) polypyridyl complexes, with novel silane functionalisation, [Ru(bipy)(2)(bipy-sil)] (PF6)(2) (3), [Ru(bipy-sil)(2)Cl-2] (6), and [Ru(bipy-sil)(2)(NCS)(2)] (7) have been synthesised and tested as chromophores (dyes) in TiO2 and WO3 based dye-sensitised solar cells (DSSCs). The performance of the respective DSSCs were compared to analogous dyes with ionic carboxylate ([Ru(bipy)(2)(dcbipy)](PF6)(2) (1), [Ru(dcbipy)(2)Cl-2] (4), [Ru(dcbipy)(2)(NCS)(2)] (5)) or phosphonate ([Ru(bipy)(2)(dpipy)](PF6)(2) (2)) linking groups. The covalent silane-metal oxide linkage offers much needed improvement to the operating conditions, and lifetime of DSSCs, in terms of pH range and choice of solvent. UV-Vis spectroscopy of the deep-red solutions showed that the bis-bipy-sil complexes absorbed more visible light than the tris-bipy complex, as indicated by the presence of two absorption bands and higher E values. The UV-Vis spectrum of (3) contained a single broad absorption at 400-600 nm with: lambda(max) = 457 nm; epsilon = 10520 +/- 440 L mol(-1) cm(-1), whereas two intense broad absorption bands were observed for novel bis-bipy-sil complexes (6): 340-370 nm (lambda(max(1)) = 365 nm, epsilon((1)) = 12716 +/- 180 L mol(-1) cm(-1)); and 440-540 nm (lambda(max(2)) = 485 nm, epsilon((2)) = 11070 +/- 150 L mol(-1) cm(-1)), and (7): 340-400 nm (lambda(max) = 371 nm epsilon((1)) = 20690 +/- 485 L mol(-1) cm(-1)), and 460-530 nm (lambda(max) = 500 nm and epsilon((2)) = 20750 +/- 487 L mol(-1) cm(-1)). The bands in (7) being significantly more defined.A 10-fold improvement in the efficiency of the bipy-sil TiO2-based DSSCs was observed from (3) to (6) to (7). This performance was lower than that of the commercial N3 dye, [Ru(dcbipy)(2)(NCS)(2)] (5), but the current of (7) on WO3, was comparable to that of the carboxylate system (4). There is considerable potential for further improvement by modification of the silyl linker, reducing the long non-conjugated propyl chain between the amide group and the silatrane (bipy-sil), to a short, conjugated link. During an extensive synthetic study, the most promising strategy was identified as direct linkage, the formation of a direct Si-C bond, using butyllithium with 4,4'-dibromo-2,2'-bipyridine and either trimethylsilane or 1-ethoxysilatrane, provided that the product can be captured and stabilised prior to binding to a metal oxide coated DSSC substrate. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.07.078

文献信息

• Direct Evidence for a Sequential Electron Transfer–Proton Transfer Mechanism in the PCET Reduction of a Metal Hydroxide Catalyst
  作者：Matthew C. Kessinger、Jeremiah Xu、Kai Cui、Quentin Loague、Alexander V. Soudackov、Sharon Hammes-Schiffer、Gerald J. Meyer

  DOI：10.1021/jacs.3c10742

  日期：2024.1.24

  for the PCET reduction reaction were quantified by nanosecond transient absorption spectroscopy as a function of solution pH and applied potential. Data acquired at pH = 5–10 revealed a stepwise electron transfer–proton transfer (ET–PT) mechanism, while kinetic measurements made below pKa(RuIII–OH/OH2) = 1.3 were used to study the analogous interfacial reaction, where electron transfer was the only

  通过独立电子转移 (ET) 和质子转移 (PT) 步骤的动力学解析，确定了反应 M ox –OH + e – + H + → M red –OH 2的质子耦合电子转移 (PCET) 机制。感兴趣的反应是由 [Ru II (tpy)(bpy')H 2 O] 2+ 、Ru II –OH 2的可见光激发引发的，其中 tpy 是 2,2':6',2"-三联吡啶， bpy' 是 4,4'-二氨基丙基硅特拉烷-2,2'-联吡啶，固定在水溶液中的 In 2 O 3 :Sn (ITO) 薄膜上。 PCET 还原反应的界面动力学通过纳秒瞬态吸收光谱定量，作为溶液 pH 值和施加电势的函数。在 pH = 5–10 下获取的数据揭示了逐步电子转移-质子转移 (ET-PT) 机制，而低于 p Ka (Ru III –OH/OH 2 ) = 1.3的动力学测量用于研究类似的界面反应，其中电子转移是唯一的机械步骤。使