fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(1,10-phenanthroline)](PF6) | 850534-70-2

• 英文名称: fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(1,10-phenanthroline)](PF6)
• 英文别名: fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(1,10-phenanthroline)]PF6；fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(phen)]PF6
• CAS: 850534-70-2
• 化学式: C₂₄H₁₇N₃O₃Re*F₆P
• 分子量: 726.588
• InChiKey: ZIDPNOAITUFFAE-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 、 1,10-菲罗啉 、 五羰基氯铼(I) 、 2,6-二甲基苯基异腈 在 AgCF₃SO₃ 作用下， 以 乙醇 为溶剂， 以97%的产率得到fac-[Re(CO)3(2,6-dimethylphenylisocyanide)(1,10-phenanthroline)](PF6)
  参考文献：
  名称：

  A spectroscopic and computational study on the effects of methyl and phenyl substituted phenanthroline ligands on the electronic structure of Re(i) tricarbonyl complexes containing 2,6-dimethylphenylisocyanide

  摘要：

  [Re(CO)3(CNx)(L)]+，其中 CNx = 2,6-二甲基苯基异氰化物，与 L = 1,10-菲咯啉 (1)、4-甲基-1,10-菲咯啉 (2)、4,7-二甲基-1,10-菲咯啉 (3)、3,4,7,8-四甲基-1,10-菲咯啉 (4)、2,9-二甲基-1,10-菲咯啉 (5) 和 2,9-二甲基-4,7-二苯基-1,10-菲咯啉 (6) 形成配合物。金属-配体-配体电荷转移跃迁 (MLLCT) 吸收带遵循以下系列：3 (27,800 cm−1) > 1、2、4 和 5 (27,500 cm−1) > 6 (26,600 cm−1)。密度泛函理论 (DFT) 几何优化揭示了 5 和 6 的 Re–N (L) 距离分别为 2.28 和 2.27 Å，而 1–4 的 Re–N (L) 距离为 2.23 Å。可逆还原电位 (E1/2(red)) 1–4 与 B3LYP 计算的 LUMO 能量线性相关。含时 (TD) DFT 和类导体可极化连续模型 (CPCM) 计算的单重激发态与实验吸收最大值的偏差不超过 700 cm−1，有助于光谱归属。3MLLCT 发射态能量在 1–6 的 77 K 发射能量范围内，误差在 900 cm−1 以内。77 K 发射能量、E1/2(red) 以及室温发射量子产率 (ϕLUMOem) 按以下顺序递减：1 > 2 > 3 > 4，而 LUMO 能量和室温发射能量则相反。发射寿命 (τem) 按以下顺序递减：3 > 4 > 2 > 1 > 5，其中 3 在室温下的发射寿命值最高，为 26.9 μs，在 77 K 下为 384 μs，而配合物 5 的发射寿命最低，室温下为 4.6 μs，77 K 下为 61 μs。

  DOI：

  10.1039/b415079a

文献信息

• Photophysical, Spectroscopic, and Computational Studies of a Series of Re(I) Tricarbonyl Complexes Containing 2,6-Dimethylphenylisocyanide and 5- and 6-Derivatized Phenanthroline Ligands
  作者：John M. Villegas、Stanislav R. Stoyanov、Wei Huang、D. Paul Rillema

  DOI：10.1021/ic048786f

  日期：2005.4.1

  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.