[Re(CO)3(dppz)(NC5H4CH2CH2COOH)]Cl | 1350263-52-3

• 英文名称: [Re(CO)3(dppz)(NC5H4CH2CH2COOH)]Cl
• 英文别名: [Re(CO)3(dipyrido[3,2-a:2',3'-c]phenazine)(3-(pyridin-4-yl)propanoic acid)]Cl
• CAS: 1350263-52-3
• 化学式: C₂₉H₁₉N₅O₅Re*Cl
• 分子量: 739.16
• InChiKey: IBHYJKDHFWVCLS-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  [Re(CO)3(dppz)(NC5H4CH2CH2COOH)]Cl 在 [C₆H₄N₃OC(N(CH₃)2)2]PF₆ 、 1-hydroxybenzotriazole hydrate 、 ((CH₃)2CH)2NCH₂CH₃ 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 fac-[Re(CO)3(dipyrido[2,3-a:2',3'-c]phenazine)(NC5H4CH2CH2CONH(CH2)7NHC11H12O6N5P-5'-ACAITATACC(GACT)3)](1+)
  参考文献：
  名称：

  Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)₃(dppz)(py)]⁺–DNA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy

  摘要：

  The complex [Re(CO)(3)(dppz)(py'-OR)](+) (dppz = dipyrido[3,2-a:2',3'-c]phenazine; py'-OR = 4-functionalized pyridine) offers IR sensitivity and can oxidize DNA directly from the excited state, making it a promising probe for the study of DNA-mediated charge transport (CT). The behavior of several covalent and noncovalent Re-DNA constructs was monitored by time-resolved IR (TRIR) and UV/visible spectroscopies, as well as biochemical methods, confirming the long-range oxidation of DNA by the excited complex. Optical excitation of the complex leads to population of MLCT and at least two distinct intraligand states. Experimental observations that are consistent with charge injection from these excited states include similarity between long-time TRIR spectra and the reduced state spectrum observed by spectroelectrochemistry, the appearance of a guanine radical signal in TRIR spectra, and the eventual formation of permanent guanine oxidation products. The majority of reactivity occurs on the ultrafast time scale, although processes dependent on slower conformational motions of DNA, such as the accumulation of oxidative damage at guanine, are also observed. The ability to measure events on such disparate time scales, its superior selectivity in comparison to other spectroscopic techniques, and the ability to simultaneously monitor carbonyl ligand and DNA IR absorption bands make TRIR a valuable tool for the study of CT in DNA.

  DOI：

  10.1021/ja205568r
• 作为产物：
  描述：

  fac-[Re(CO)3(dipyrido[2,3-a:2',3'-c]phenazine)(3-(pyridin-4-yl)propanoic acid)]PF6 在 Sephadex A-25 resin 作用下， 以 not given 为溶剂， 生成 [Re(CO)3(dppz)(NC5H4CH2CH2COOH)]Cl
  参考文献：
  名称：

  Charge Photoinjection in Intercalated and Covalently Bound [Re(CO)₃(dppz)(py)]⁺–DNA Constructs Monitored by Time-Resolved Visible and Infrared Spectroscopy

  摘要：

  The complex [Re(CO)(3)(dppz)(py'-OR)](+) (dppz = dipyrido[3,2-a:2',3'-c]phenazine; py'-OR = 4-functionalized pyridine) offers IR sensitivity and can oxidize DNA directly from the excited state, making it a promising probe for the study of DNA-mediated charge transport (CT). The behavior of several covalent and noncovalent Re-DNA constructs was monitored by time-resolved IR (TRIR) and UV/visible spectroscopies, as well as biochemical methods, confirming the long-range oxidation of DNA by the excited complex. Optical excitation of the complex leads to population of MLCT and at least two distinct intraligand states. Experimental observations that are consistent with charge injection from these excited states include similarity between long-time TRIR spectra and the reduced state spectrum observed by spectroelectrochemistry, the appearance of a guanine radical signal in TRIR spectra, and the eventual formation of permanent guanine oxidation products. The majority of reactivity occurs on the ultrafast time scale, although processes dependent on slower conformational motions of DNA, such as the accumulation of oxidative damage at guanine, are also observed. The ability to measure events on such disparate time scales, its superior selectivity in comparison to other spectroscopic techniques, and the ability to simultaneously monitor carbonyl ligand and DNA IR absorption bands make TRIR a valuable tool for the study of CT in DNA.

  DOI：

  10.1021/ja205568r

文献信息

• Using Metal Complex Reduced States to Monitor the Oxidation of DNA
  作者：Eric D. Olmon、Michael G. Hill、Jacqueline K. Barton

  DOI：10.1021/ic201511y

  日期：2011.12.5

  Metallointercalating photooxidants interact intimately with the base stack of double-stranded DNA and exhibit rich photophysical and electrochemical properties, making them ideal probes for the study of DNA-mediated charge transport (CT). The complexes [Rh(phi)(2)(bPy')](3+) (phi = 9,10-phenanthrenequinone diimine; bpy' = 4-methyl-4'-(butyric acid)-2,2'-bipyridine), [Ir(ppy),(dppz')](+) (ppy = 2-phenylpyridine; dppz' = 6-(dipyrido [3,2-a:2',3'-c]phenazin-11-yl)hex-5-ynoic acid), and [Re(CO)(3)(dppz)(py')](+) (dppz = dipyrido[2,3-a:2',3'-c]phenazine; py' = 3-(pyridin-4-yl)-propanoic acid) were each covalently tethered to DNA to compare their photooxidation efficiencies. Biochemical studies show that upon irradiation, the three complexes oxidize guanine by long-range DNA-mediated CT with the efficiency: Rh > Re > Ir. Comparison of spectra obtained by spectroelectrochemistry after bulk reduction of the free metal complexes with those obtained by transient absorption (TA) spectroscopy of the conjugates suggests that the reduced metal states form following excitation of the conjugates at 355 nm. Electrochemical experiments and kinetic analysis of the TA decays indicate that the thermodynamic driving force for CT, variations in the efficiency of back electron transfer, and coupling to DNA are the primary factors responsible for the trend observed in the guanine oxidation yields of the three complexes.