Re(dipyrido[3,2-a:2',3'-c]phenazine)(CO)3(OTf) | 231934-50-2

• 英文名称: Re(dipyrido[3,2-a:2',3'-c]phenazine)(CO)3(OTf)
• 英文别名: Re(dipyrido[3,2-a:2',3'-c]phenazine)(CO)₃(OTf)；Re(dppz)(CO)₃(OTf)；fac-[rhenium(I)(dipyrido[3,2-a:2',3'-c]phenazine)(CO)3(trifluoromethane sulfonato)]
• CAS: 231934-50-2
• 化学式: C₂₂H₁₀F₃N₄O₆ReS
• 分子量: 701.613
• InChiKey: XJRMTLMJBRCMBH-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  10-(4-picolyl)phenothiazine 、 Re(dipyrido[3,2-a:2',3'-c]phenazine)(CO)3(OTf) 以 甲醇 为溶剂， 以40%的产率得到fac-[rhenium(I)(dipyrido[3,2-a:2',3'-c]phenazine)(CO)3(10-(4-picolyl)phenothiazine)] hexafluorophosphate
  参考文献：
  名称：

  Excited State Competition in fac-[Re^I(dppz)(CO)₃(py-PTZ)]⁺

  摘要：

  Following Re-I --> dppz (dppz is dipyrido[3,2-a:2',3'-c]phenazine) metal-to-ligand charge transfer (MLCT) excitation of fac-[Re(dppz)(CO)(3)(py-PTZ)](+) (py-PTZ is 10-(4-picolyl)phenothiazine), there is a dynamic competition between intramolecular electron and energy transfer. Laser flash photolysis at 420 nm in 1,2-dichloroethane produces the MLCT excited state fac-[Re-II(dppz(.-))(CO)(3)(py-PTZ)](+)*. It undergoes intramolecular energy transfer to give the dppz-localized pi pi* excited state [Re-I((3)dppz)*(CO)(3)(py-PTZ)](+) (3 pi pi*) in competition with electron transfer to give the redox-separated state (RS) [Re-I(dppz(.-))(CO)(3)(py-PTZ(.+))](+). The pi pi* state decays to the ground state with k = 1.7 x 10(4) s(-1) (tau = 60 +/- 15 mu s) and the RS state decays with k = 9.1 x 10(6) s(-1) (tau = 110 +/- 10 ns). The competition ratio for formation of the two is [RS]/[(3)pi pi*] similar to 2.4. Subsequent (3)pi pi* --> RS interconversion is slow oven though the process is favored by 0.43 eV.

  DOI：

  10.1021/jp990543z
• 作为产物：
  描述：

  silver trifluoromethanesulfonate 、 Re(dipyrido[3,2-a:2′,3′-c]phenazine) 以 四氢呋喃 为溶剂， 以95.3%的产率得到Re(dipyrido[3,2-a:2',3'-c]phenazine)(CO)3(OTf)
  参考文献：
  名称：

  Excited State Competition in fac-[Re^I(dppz)(CO)₃(py-PTZ)]⁺

  摘要：

  Following Re-I --> dppz (dppz is dipyrido[3,2-a:2',3'-c]phenazine) metal-to-ligand charge transfer (MLCT) excitation of fac-[Re(dppz)(CO)(3)(py-PTZ)](+) (py-PTZ is 10-(4-picolyl)phenothiazine), there is a dynamic competition between intramolecular electron and energy transfer. Laser flash photolysis at 420 nm in 1,2-dichloroethane produces the MLCT excited state fac-[Re-II(dppz(.-))(CO)(3)(py-PTZ)](+)*. It undergoes intramolecular energy transfer to give the dppz-localized pi pi* excited state [Re-I((3)dppz)*(CO)(3)(py-PTZ)](+) (3 pi pi*) in competition with electron transfer to give the redox-separated state (RS) [Re-I(dppz(.-))(CO)(3)(py-PTZ(.+))](+). The pi pi* state decays to the ground state with k = 1.7 x 10(4) s(-1) (tau = 60 +/- 15 mu s) and the RS state decays with k = 9.1 x 10(6) s(-1) (tau = 110 +/- 10 ns). The competition ratio for formation of the two is [RS]/[(3)pi pi*] similar to 2.4. Subsequent (3)pi pi* --> RS interconversion is slow oven though the process is favored by 0.43 eV.

  DOI：

  10.1021/jp990543z

文献信息

• Defining Electronic Excited States Using Time-Resolved Infrared Spectroscopy and Density Functional Theory Calculations
  作者：Dana M. Dattelbaum、Kristin M. Omberg、P. Jeffrey Hay、Nouvelle L. Gebhart、Richard L. Martin、Jon R. Schoonover、Thomas J. Meyer

  DOI：10.1021/jp037096e

  日期：2004.4.1

  Characteristic patterns of infrared bands in the 7,(CO) region have been observed in the time-resolved infrared (TRIR) spectra of fac-rhenium tricarbonyl complexes that allow for identification of transient states that result following laser flash excitation. These patterns can be interpreted by combining experimental TRIR data with density functional theory (DFT) calculations. The DFT calculations are particularly valuable as they provide vibrational energy shifts between the ground and excited states and an analysis of the electronic interactions in terms of the orbitals involved in the excitation. TRIR and DFT results for four different transient excited states. intraligand pi -->pi*, metal-to-ligand charge transfer (MLCT), intramolecular (dpi-Opi) --> pi* excited states, and a redox-separated (RS state), are presented here. A unique example of competing excited states Studied by TRIR is also presented. The complexes studied include fac-[Re-1(CO)3(Me(2)dppz)(4-Etpy)](+), fac-[Re-1(CO)(3)(bpy)(4-Etpy)](+),fac-[Re-1(CO)(3)(4,4'-(CH3)(2)bpy)(OQD)],fac-[Re-1(CO)(3)(Me(2)dppz)(py-PTZ)](+), and fac-[Re-1(CO)(3)(dppz)(py-PTZ)](+) (Me(2)ppz is dimethyl dipyrido[3,2-a:2',3'-c]phenazine; dppz is dipyrido[3,2-a:2',3'-c]phenazine; 4Etpy is 4-ethylpyridine; bpy is 2,2'-bipyridine; 4,4'-(CH3)(2)bpy is 4,4'-(CH3)-2,2'bipyridine: OQD is 1-methyl-6-oxyquinone; py-PTZ is 10-(4-picolyl)phenothiazine). In addition to the DFT studies on the lowest triplet states probed by TRIR spectroscopy, time-dependent DFT (TD-DFT) calculations were also performed to analyze several of the lowest singlet and triplet excited states for each of the complexes.