[((Me)2bpb)Ru(NO)(Cl)] | 732283-04-4

• 英文名称: [((Me)2bpb)Ru(NO)(Cl)]
• 英文别名: chloro(1,2-bis(pyridine-2-carboximido)-4,5-dimethylbenzene(-2H))nitrosylruthenium(II)；[((Me)₂bpb)Ru(NO)(Cl)]；[(1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene(2-))Ru(NO)(Cl)]；[(1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene)Ru(NO)Cl]
• CAS: 732283-04-4
• 化学式: C₂₀H₁₆ClN₅O₃Ru
• 分子量: 510.902
• InChiKey: RRJXNGIUFPMVHS-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：
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• 拓扑面积：
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• 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：

  [((Me)2bpb)Ru(NO)(Cl)] 、 乙基荧光素 在 AgBF₄ 、 NaH 作用下， 以 乙腈 为溶剂， 以41%的产率得到[(1,2-bis(pyridine-2-carboxamido)-4,5-dimethylbenzene)Ru(NO)(fluorescein ethyl ester)]
  参考文献：
  名称：

  Triggered Dye Release via Photodissociation of Nitric Oxide from Designed Ruthenium Nitrosyls: Turn-ON Fluorescence Signaling of Nitric Oxide Delivery

  摘要：

  Two new fluorescein-tethered nitrosyls derived from designed tetradentate ligands with carboxamido-N donors have been synthesized and characterized by spectroscopic techniques. These two diamagnetic {Ru-NO}(6) nitrosyls, namely, [(Me(2)bpb)Ru(NO)(FlEt)] (1-FlEt, Me(2)bpb = 1,2-bis(pyridine-2-carboxamido)5-dimethylbenzene, FlEt = fluorescein ethyl ester) and [((OMe)(2)IQ1)Ru(NO)(FlEt)] (2-FlEt, (OMe)(2)IQ1 = 1,2-bis(isoquinoline-1-carboxamido)-4,5-dimethoxybenzene), display NO stretching frequencies (nu(NO)) at 1846 and 1832 cm(-1) in addition to their FlEt carbonyl stretching frequencies (nu(CO)) at 1715 and 1712 cm(-1), respectively. Coordination of the dye ligand enhances the absorptivity and NO photolability of these two nitrosyls in the visible region (450-600 nm) of light. Exposure to visible light promotes rapid loss of NO from both {Ru-NO}(6) nitrosyls to generate Ru(III) photoproducts in dry aprotic solvents, such as MeCN and DMF. The FlEt(-) moiety remains bound to the paramagnetic Ru(III) center such gases, and hence, the photoproducts exhibit very weak fluorescence from the dye unit. In the presence of water, the Ru(III) photoproducts undergo further aquation and loss of the FlEt(-) moiety via protonation. These steps lead to turn-ON fluorescence (from the free FlEt unit) and provide a visual signal of the NO photorelease from 1-FlEt and 2-FlEt in aqueous media.

  DOI：

  10.1021/ic201242d

文献信息

• Photosensitization via Dye Coordination:  A New Strategy to Synthesize Metal Nitrosyls That Release NO under Visible Light
  作者：Michael J. Rose、Marilyn M. Olmstead、Pradip K. Mascharak

  DOI：10.1021/ja070247x

  日期：2007.5.1

  Direct coordination of the dye resorufin (Resf) to the ruthenium center photosensitizes the Ru−NO bond and improves NO photolability of the designed Ru−NO}6 nitrosyl [(Me2bpb)Ru(NO)(Resf)] under visible light.

  染料试卤灵 (Resf) 与钌中心的直接配位使 Ru-NO 键光敏化，并提高了设计的 Ru-NO}6 亚硝酰基 [(Me2bpb)Ru(NO)(Resf)] 在可见光下的 NO 光稳定性。
• Evidence of dexter energy transfer in NO photolability of dye-sensitized ruthenium nitrosyls
  作者：Tara R. deBoer-Maggard、Nicole L. Fry、Pradip K. Mascharak

  DOI：10.1016/j.ica.2013.04.034

  日期：2013.9

  Direct attachment of light-harvesting dye molecules to the ruthenium center of designed Ru-NO}(6) nitrosyls has been shown to exhibit enhanced light-induced NO photorelease upon exposure to visible light. Theoretical studies have indicated that orbital overlap between the MOs of the dye and the nitrosyl units are key for such sensitization. In order to check whether altering the electronic conjugation between these two units causes reduction in the extent of sensitization, we have synthesized a pyridinyloxy-fluorescein dye PyFlEt and attached it to two designed ruthenium nitrosyls through the pyridine-N donor of the pyridinyloxy-end. The quantum yield values of NO photodissociation at 500 nm (phi(NO)) and fluorescence quantum yield values (phi(Fl)) of these two nitrosyl-dye conjugates namely, [(Me)(2)bpb)Ru(NO)(PyFlEt)]ClO4 (1-PyFlEt) and [((OMe)(2)IQ1)Ru(NO)(PyFlEt)]BF4 (2-PyFlEt) have been compared with those of [(Me)(2)bpb)Ru(NO)(FlEt)]ClO4 (1-FlEt) and [((OMe)(2)IQ1)Ru(NO)(FlEt)]BF4 (2-FlEt) in which the same FlEt dye is directly attached through the phenolato-O donor. This minor alteration in the linkage between the dye and the nitrosyl unit has caused significant reduction in the phi(NO) values of 1-PyFlEt and 2-PyFlEt while their phi(Fl) values have shown moderate improvement. These results strongly suggest that the light energy absorbed by the dye unit is transferred to the Ru-NO moiety through the Dexter pathway. If the electronic overlap is disrupted, only part of the energy is used in NO photorelease and a significant portion is lost through fluorescence. (C) 2013 Elsevier B. V. All rights reserved.
• Incorporation of a Designed Ruthenium Nitrosyl in PolyHEMA Hydrogel and Light-Activated Delivery of NO to Myoglobin
  作者：Genevieve M. Halpenny、Marilyn M. Olmstead、Pradip K. Mascharak

  DOI：10.1021/ic700694b

  日期：2007.8.1

  A ruthenium nitrosyl with 4-vinylpyridine (4-vpy) as one ligand, namely, [Ru(Me(2)bpb)(NO)(4-vpy)](BF4) (1), has been synthesized and structurally characterized. This diamagnetic Ru-NO}(6) nitrosyl is photoactive and readily releases NO upon exposure to low-intensity (5-10 mW) UV light (quantum yield at 300 nm = 0.18). Radical-induced copolymerization of 2-hydroxyethyl methacrylate (HEMA) and ethyleneglycol dimethacrylate (EGDMA) in the presence of 1 has afforded a 1-pHEMA, a transparent hydrogel in which 1 is covalently attached to the polymer backbone. Exposure of 1-pHEMA to UV light (5-10 mW) results in rapid release of NO (detected by NO electrode) that can be delivered to biological targets such as myoglobin. The photoactivity of 1-pHEMA is strictly dependent on exposure to UV light.