13-Bromo-11-(trifluoromethyl)quinoxalino[2,3-f][1,10]phenanthroline | 1570131-17-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 13-Bromo-11-(trifluoromethyl)quinoxalino[2,3-f][1,10]phenanthroline
• 英文别名: 13-bromo-11-(trifluoromethyl)quinoxalino[2,3-f][1,10]phenanthroline
• CAS: 1570131-17-7
• 化学式: C₁₉H₈BrF₃N₄
• 分子量: 429.199
• InChiKey: AEUBEQNYRVJWRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  27
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  五羰基氯铼(I) 、 13-Bromo-11-(trifluoromethyl)quinoxalino[2,3-f][1,10]phenanthroline 以 乙醇 为溶剂， 以92%的产率得到fac-chlorotricarbonyl (13-bromo-11-trimethyldipyrido[3,2-a:2′,3′-c]phenazine)rhenium
  参考文献：
  名称：

  Re(I) Complexes of Substituted dppz: A Computational and Spectroscopic Study

  摘要：

  A series of dipyrido[3,2-a:2',3'-c]phenazine (dppz)-based ligands with electron-withdrawing substituents and their [Re(CO)(3)(L)Cl] and [Re(CO)(3)(L)(py)]PF6 complexes have been studied using Raman, resonance Raman, and transient resonance Raman (TR2) and time-resolved infrared (TRIR) spectroscopic techinques in conjunction with computational chemistry as well as electrochemical studies, emission, and absorption of ground and excited states. DFT (B3LYP) frequency calculations show good agreement with nonresonant Raman spectra, which allowed these to be used to identify phenanthroline, phenazine, and delocalized modes. These band assignments were used to establish the nature of chromophores active in resonance Raman spectra, probed with wavelengths between 350.7 and 457.9 nm. X-ray crystallography of [Re(CO)(3)(dppzBr(2))Cl] and [Re(CO)(3)(dppzBr)(py)PF6 showed these crystallize in space groups triclinic P1 and monoclinic P2(1/n), respectively. Electrochemical studies showed that substituents have a strong effect on the phenazine MO, changing the reduction potential by 200 mV. Transient absorption studies showed that generally the [Re(CO)(3)(L)(py)]PF6 complexes had longer lifetimes than the corresponding [Re(CO)(3)(L)Cl] complexes; the probed state is likely to be pi -> pi* (phz) in nature. TR2 spectra of the ligands provided a marker for the triplet pi -> pi* state, and the TR2 spectra of the complexes suggest an intraligand (IL) pi,pi* state for [Re(CO)(3)(L)(py)](+) complexes, and a potentially mixed IL/MLCT state for [Re(CO)(3)(L)Cl] complexes. TRIR spectroscopy is more definitive with THEXI state assignments, and analysis of the metal-carbonyl region (1800-2100 cm(-1)) on the picosecond and nanosecond time scales indicates the formation of MLCT(phen/phz) states for all [Re(CO)(3)(L)Cl] complexes, and IL pi -> pi* (phen) states for all [Re(CO)(3)(L)(py)](+) complexes, with all but [Re(CO)(3)(dppzBr(CF3))(py)(+) showing some contribution from an MLCT(phen) state also.

  DOI：

  10.1021/ic403056g
• 作为产物：
  描述：

  1,10-邻二氮杂菲-5,6-二酮 、 3-溴-5-三氟甲基-1,2-苯二胺 以 乙醇 为溶剂， 反应 8.0h， 以89%的产率得到13-Bromo-11-(trifluoromethyl)quinoxalino[2,3-f][1,10]phenanthroline
  参考文献：
  名称：

  Re(I) Complexes of Substituted dppz: A Computational and Spectroscopic Study

  摘要：

  A series of dipyrido[3,2-a:2',3'-c]phenazine (dppz)-based ligands with electron-withdrawing substituents and their [Re(CO)(3)(L)Cl] and [Re(CO)(3)(L)(py)]PF6 complexes have been studied using Raman, resonance Raman, and transient resonance Raman (TR2) and time-resolved infrared (TRIR) spectroscopic techinques in conjunction with computational chemistry as well as electrochemical studies, emission, and absorption of ground and excited states. DFT (B3LYP) frequency calculations show good agreement with nonresonant Raman spectra, which allowed these to be used to identify phenanthroline, phenazine, and delocalized modes. These band assignments were used to establish the nature of chromophores active in resonance Raman spectra, probed with wavelengths between 350.7 and 457.9 nm. X-ray crystallography of [Re(CO)(3)(dppzBr(2))Cl] and [Re(CO)(3)(dppzBr)(py)PF6 showed these crystallize in space groups triclinic P1 and monoclinic P2(1/n), respectively. Electrochemical studies showed that substituents have a strong effect on the phenazine MO, changing the reduction potential by 200 mV. Transient absorption studies showed that generally the [Re(CO)(3)(L)(py)]PF6 complexes had longer lifetimes than the corresponding [Re(CO)(3)(L)Cl] complexes; the probed state is likely to be pi -> pi* (phz) in nature. TR2 spectra of the ligands provided a marker for the triplet pi -> pi* state, and the TR2 spectra of the complexes suggest an intraligand (IL) pi,pi* state for [Re(CO)(3)(L)(py)](+) complexes, and a potentially mixed IL/MLCT state for [Re(CO)(3)(L)Cl] complexes. TRIR spectroscopy is more definitive with THEXI state assignments, and analysis of the metal-carbonyl region (1800-2100 cm(-1)) on the picosecond and nanosecond time scales indicates the formation of MLCT(phen/phz) states for all [Re(CO)(3)(L)Cl] complexes, and IL pi -> pi* (phen) states for all [Re(CO)(3)(L)(py)](+) complexes, with all but [Re(CO)(3)(dppzBr(CF3))(py)(+) showing some contribution from an MLCT(phen) state also.

  DOI：

  10.1021/ic403056g

文献信息

• Re(I) Complexes of Substituted dppz: A Computational and Spectroscopic Study
  作者：Holly van der Salm、Michael G. Fraser、Raphael Horvath、Scott A. Cameron、Jonathan E. Barnsley、Xue-Zhong Sun、Michael W. George、Keith C. Gordon

  DOI：10.1021/ic403056g

  日期：2014.3.17

  A series of dipyrido[3,2-a:2',3'-c]phenazine (dppz)-based ligands with electron-withdrawing substituents and their [Re(CO)(3)(L)Cl] and [Re(CO)(3)(L)(py)]PF6 complexes have been studied using Raman, resonance Raman, and transient resonance Raman (TR2) and time-resolved infrared (TRIR) spectroscopic techinques in conjunction with computational chemistry as well as electrochemical studies, emission, and absorption of ground and excited states. DFT (B3LYP) frequency calculations show good agreement with nonresonant Raman spectra, which allowed these to be used to identify phenanthroline, phenazine, and delocalized modes. These band assignments were used to establish the nature of chromophores active in resonance Raman spectra, probed with wavelengths between 350.7 and 457.9 nm. X-ray crystallography of [Re(CO)(3)(dppzBr(2))Cl] and [Re(CO)(3)(dppzBr)(py)PF6 showed these crystallize in space groups triclinic P1 and monoclinic P2(1/n), respectively. Electrochemical studies showed that substituents have a strong effect on the phenazine MO, changing the reduction potential by 200 mV. Transient absorption studies showed that generally the [Re(CO)(3)(L)(py)]PF6 complexes had longer lifetimes than the corresponding [Re(CO)(3)(L)Cl] complexes; the probed state is likely to be pi -> pi* (phz) in nature. TR2 spectra of the ligands provided a marker for the triplet pi -> pi* state, and the TR2 spectra of the complexes suggest an intraligand (IL) pi,pi* state for [Re(CO)(3)(L)(py)](+) complexes, and a potentially mixed IL/MLCT state for [Re(CO)(3)(L)Cl] complexes. TRIR spectroscopy is more definitive with THEXI state assignments, and analysis of the metal-carbonyl region (1800-2100 cm(-1)) on the picosecond and nanosecond time scales indicates the formation of MLCT(phen/phz) states for all [Re(CO)(3)(L)Cl] complexes, and IL pi -> pi* (phen) states for all [Re(CO)(3)(L)(py)](+) complexes, with all but [Re(CO)(3)(dppzBr(CF3))(py)(+) showing some contribution from an MLCT(phen) state also.