[(4’-di-p-anisylamino-2,2’:6’,2’’-terpyridine)RuCl_3] | 1375960-06-7

• 英文名称: [(4’-di-p-anisylamino-2,2’:6’,2’’-terpyridine)RuCl_3]
• 英文别名: [Ru(4′-(di-p-anisylamino)-2,2':6',2''-terpyridine)Cl₃]；Ru(4'-di-(p-methoxyphenyl)amino-2,2':6',2''-terpyridine)Cl₃；Ru(daatpy)Cl₃；RuCl₃(daatpy)；[Ru(Ntpy)Cl₃]；[RuCl3(4'-di-p-anisylamino-2,2':6',2''-terpyridine)]
• CAS: 1375960-06-7
• 化学式: C₂₉H₂₄Cl₃N₄O₂Ru
• 分子量: 667.964
• InChiKey: KGCBQDKNCRXUDK-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  六氟磷酸钾 、 [(4’-di-p-anisylamino-2,2’:6’,2’’-terpyridine)RuCl_3] 、 4'-<4-(N,N-di-p-anisylamino)phenyl>-2,2':6',2''-terpyridine 以 水 为溶剂， 反应 0.5h， 以54%的产率得到[Ru(4′-(di-p-anisylamino)-2,2′:6′,2″-terpyridine)(4′-(di-p-anisylaminophen-4-yl)-2,2′:6′,2″-terpyridine)](PF₆)₂
  参考文献：
  名称：

  钌-双-叔吡啶配合物与两种氧化还原-不对称胺取代基：电荷转移方向的电位控制反转

  摘要：

  制备了带有两个氧化还原不对称胺单元的钌-双-三联吡啶络合物[Ru（NPhtpy）（Ntpy）] 2+（2 2+），其中NPhtpy为4'-（二-对-茴香基氨基酚-4-基）-2，2′：6′，2″-吡啶和Ntpy是4′-（二-对-茴香基氨基）-2，2′：6′，2″-吡啶。该络合物在相对于Ag / AgCl的+0.82和+1.02 V下显示两个连续的氧化还原对，分别被分配给NPhtpy和Ntpy配体的胺组分的N •+ / 0过程。通过氧化电解获得的单氧化络合物2 3+表明存在从钌（II）到NPhtpy配体（MN的氧化的铝自由基阳离子）的电荷转移NPhtpy CT）约为1000 nm。在二氧化形式（2 4+）中，MN NPhtpy CT跃迁明显减少，并且在1380 nm处出现了从钌（II）到Ntpy配体（MN Ntpy CT）氧化的铝自由基阳离子的相反电荷转移。络合物[Ru（NPhtpy）（tpy）]

  DOI：

  10.1021/om500904k

文献信息

• A Combined Experimental and Computational Study of Linear Ruthenium(II) Coordination Oligomers with End-Capping Organic Redox Sites: Insight into the Light Absorption and Charge Delocalization
  作者：Chang-Jiang Yao、Ren-Hui Zheng、Hai-Jing Nie、Bin-Bin Cui、Qiang Shi、Jiannian Yao、Yu-Wu Zhong

  DOI：10.1002/chem.201301319

  日期：2013.9.9

  Two series of linear ruthenium coordination oligomers, [(Ntpy)Run(tppz)n−1(tpy)]2n+ (mono‐Ntpy series, n=1–3) and [(Ntpy)2Run(tppz)n−1]2n+ (bis‐Ntpy series, n=1–3) have been prepared, where Ntpy is the capping ligand 4′‐di‐p‐anisylamino‐2,2′:6′,2′′‐terpyridine, tppz is tetra‐2‐pyridylpyrazine, and tpy is 2,2′:6′,2′′‐terpyridine. The electrochemical measurements evidence oxidation events from both the

  两个系列的线性钌配位低聚物，[（Ntpy）Ru n（tppz）n -1（tpy）] 2 n +（单Ntpy系列，n = 1–3）和[（Ntpy）2 Ru n（tppz）n -1 ] 2 n +（bis-Ntpy系列，n = 1–3）已经准备好，其中Ntpy是封端配体4'-di- p-茴香基氨基-2,2'：6'，2''-吡啶，tppz是四-2-吡啶基吡嗪，tpy是2,2'：6'，2''-吡啶 电化学测量结果表明，胺链段和金属中心都发生了氧化事件，tppz和封端配体产生了还原波。相对于没有末端胺单元的模型复合物，两种系列的复合物均显示出大大增强的光吸收。对两个序列都进行了密度泛函理论（DFT）计算，对双Ntpy系列化合物（n = 1–4）进行了与时间有关的DFT（TD‐DFT）计算，以表征其电子结构和激发态并预测长链聚合物的电子性能。单电子氧化后，单Ntpy系列单钌和二钌络合物显示N +近红外
• Tuning the Electronic Coupling in Cyclometalated Diruthenium Complexes through Substituent Effects: A Correlation between the Experimental and Calculated Results
  作者：Jiang-Yang Shao、Yu-Wu Zhong

  DOI：10.1002/chem.201402252

  日期：2014.7.7

  energy of the IVCT band Eop, and the ground‐state delocalization coefficient α2. Time‐dependent (TD)DFT calculations suggest that the absorptions in the visible region of 12+–62+ are mainly associated with the metal‐to‐ligand charge‐transfer transitions from both ruthenium ions and to both terminal ligands and the bridging ligand. However, the energies of these transitions vary significantly. DFT calculations

  常用的桥接配体3,3'，5,5'-四（N-甲基苯并咪唑-2-基）联苯和四个带有各种取代基（胺，甲苯基，硝基和酯基）的吡啶吡啶末端配体合成10个环金属化的钌络合物1 2+ – 10 2+。其中，化合物1 2+ – 6 2+是氧化还原非对称的，其他化合物是对称的。这些络合物显示出两个Ru III / II过程和单电子氧化态的间隔电荷转移（IVCT）跃迁。1 2+ – 10 2+的电势间隔（ΔE）已被相关的能量差Δ ģ 0，则IVCT带的能量ë运算，和基态的离域系数α 2。时间依赖性（TD）DFT计算表明，1 2+ – 6 2+可见光区域的吸收主要与从钌离子到末端配体和桥联的金属到配体的电荷转移跃迁有关。配体。但是，这些跃迁的能量差异很大。DFT计算已在1 2+ – 6 2+和1 3+ – 6上执行3+提供有关混合价化合物的电子结构和自旋种群的信息。TDDFT预测的IVCT激发很好地再现了跃迁能
• Cyclometalated ruthenium(ii) complexes with a bis-carbene CCC-pincer ligand
  作者：You-Ming Zhang、Jiang-Yang Shao、Chang-Jiang Yao、Yu-Wu Zhong

  DOI：10.1039/c2dt31015e

  日期：——

  The first series of cyclometalated ruthenium complexes with a CCC-pincer bis-carbene ligand have been obtained as bench-stable compounds. Single-crystal X-ray analysis of one of these complexes with 4′-di-p-anisylamino-2,2′:6′,2′′-terpyridine is presented. The RuII/III redox potentials and MLCT absorptions of these complexes can be varied by attaching an electron-donating or -withdrawing group on the noncyclometalating ligand.

  第一批带有 CCC-钳双卡宾配体的环金属化钌配合物已作为实验室稳定的化合物获得。提出了其中一种与 4'-二对茴香胺基-2,2':6',2''-三联吡啶配合物的单晶 X 射线分析。这些配合物的 RuII/III 氧化还原电位和 MLCT 吸收可以通过在非环金属化配体上连接给电子或吸电子基团来改变。
• Combined Experimental and Computational Study of Pyren-2,7-diyl-Bridged Diruthenium Complexes with Various Terminal Ligands
  作者：Chang-Jiang Yao、Hai-Jing Nie、Wen-Wen Yang、Jiannian Yao、Yu-Wu Zhong

  DOI：10.1021/ic503117k

  日期：2015.5.18

  Cyclometalated diruthenium complexes 1(PF6)(2)-5(PF6)(2) bridged by 1,3,6)8-tetra(pyrid-2-yl)-pyrene have been prepared, with the terminal ligand bis(N-methylbenzimidazolyl)pyridine (1 (PF6)(2)), 4'-di-(p-methoxyphenyl)amino-2,2':6';2,''-terpyridine (2(PF6)(2))-,4'-pmethoxyphenyl-2,2':6',2 ''-terpyridine (3(PF6)(2)), 2,2':6',2 ''-terpyridine (4(PF6)(2))) and trimethyl-4,4',4 ''-tricarboxylate-2,2':6 '',2 ''-terpyridine (5(PF6)). The single-crystal X-ray structure of 4(PF6)(2) is presented. These complexes show two stepwise anodic redox pairs, and the potentials progressively increase from 1(PF6)(2) to 5(PF6)(2). Complexes 1(PF6)(2)-4(PF6)(2) have comparable electrochemical potential splitting of 200-210 mV, while complex 5(PF6)(2) has a splitting of 170 mV. Upon one-electron oxidation by chemical oxidation or electrolysis, the resulting mixed-valent complexes 1(3+)-5(3+) display broad and intense absorptions between 1000 and 3000 nm. Complexes 1(3+) and 2(3+) show the presence of a higher-energy shoulder band in addition to the Main near-infrared absorption band. This shoulder band is less distinguished for 3(3+)-5(3+). Three-state theory has been used to explain this difference. The one-electron oxidized forms, 1(3+)-5(3+), exhibit rhombic EPR signals at 77 K with the isotropic g values in the range of 2.18-2.24. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations have been performed on 1(2+)-5(2+) to characterize their electronic structures and rationalize the absorption spectra in a wide energy range. DFT computations on 1(3+)-5(3+) show that both ruthenium ions and the bridging ligand have comparable spin densities. TDDFT computations on 1(3+) and 4(3+) have been performed to. complement the experimental results.