fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(5,6-dimethyl-1,10-phenanthroline)]PF6 | 850534-78-0

• 英文名称: fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(5,6-dimethyl-1,10-phenanthroline)]PF6
• 英文别名: fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(5,6-Me2-phen)]PF6
• CAS: 850534-78-0
• 化学式: C₂₆H₂₁N₃O₃Re*F₆P
• 分子量: 754.642
• InChiKey: ODZGSENFPVGCOV-UHFFFAOYSA-N

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

• 作为产物：
  描述：

  ammonium hexafluorophosphate 、 五羰基氯铼(I) 、 5,6-二甲基-1,10-菲咯啉 、 2,6-二甲基苯基异腈 、 silver trifluoromethanesulfonate 以 乙醇 为溶剂， 以77%的产率得到fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(5,6-dimethyl-1,10-phenanthroline)]PF6
  参考文献：
  名称：

  Photophysical, Spectroscopic, and Computational Studies of a Series of Re(I) Tricarbonyl Complexes Containing 2,6-Dimethylphenylisocyanide and 5- and 6-Derivatized Phenanthroline Ligands

  摘要：

  The ligand 2,6-dimethylphenylisocyanide (CNx) forms six complexes of the formula [Re(CO)(3)(CNx)(L)](+), where L = 1,10-phenanthroline (1), 5-chloro-1,10-phenanthroline (2), 5-nitro-1,10-phenanthroline (3), 5-methyl-1,10-phenanthroline (4), 5,6-dimethyl-1,10-phenanthroline (5), and 1,10-phenanthrolinopyrrole (6). The lowest-energy absorption peaks of the complexes red-shift in the order 1 < 2 < 3 < 4 < 5 < 6. The time-dependent density functional theory (TDDFT) and conductor-like polarizable continuum model (CPCM) computed singlet excited states in ethanol deviate by 1000 cm(-1) or less from the experimental UV-vis peaks. The complexes undergo reversible reductions and irreversible oxidations. The electronic energy gap increases in the order 3 < 2 < 1 < 4 < 5 < 6, which is the order of increasing electron-donating power of the phen substituents. The reduction potentials linearly correlate with the B3LYP calculated LUMO energies for 1-6. The complexes emit at room temperature and at 77 K except 3, which emits only at 77 K. The calculated (MLLCT)-M-3 energies are within 1100 cm(-1) from the experimental emission energies at 77 K. The 77 K emission curve-fitting analysis results agree with the computational assignment of the emitting state as 3MLLCT for 1-5 and (LC)-L-3 for 6. The experimental 77 K emission energies and the calculated (MLLCT)-M-3 state energies increase in the order 6 < 5, 3 < 2 < 4, 1. The 77 K emission lifetimes increase upon addition of substituents from 65 mu s for 1 to 171 mu s for 2, to 230 mu s for 4 and 5, and to 322 mu s for 3. The emission quantum yields at room temperature in solution are 0.77, 0.78, 0.83, 0.56, and 0.11 for complexes 1, 2, 4, 5, and 6, respectively.

  DOI：

  10.1021/ic048786f