N,N'-(9-borabicyclo[3.3.1]-non-9-yl)-5-mesityldipyrrin | 870753-34-7

• 英文名称: N,N'-(9-borabicyclo[3.3.1]-non-9-yl)-5-mesityldipyrrin
• CAS: 870753-34-7
• 化学式: C₂₆H₃₁BN₂
• 分子量: 382.357
• InChiKey: OFSXTYRJZJVOAE-SZPZYZBQSA-N

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

• 作为产物：
  描述：

  5-phenyl-4,6-dipyrrin 、 9-硼杂双环[3.3.1]壬基三氟甲磺酸酯 在 triethylamine 作用下， 以 二氯甲烷 为溶剂， 以51%的产率得到N,N'-(9-borabicyclo[3.3.1]-non-9-yl)-5-mesityldipyrrin
  参考文献：
  名称：

  Structural Control of the Photodynamics of Boron−Dipyrrin Complexes

  摘要：

  Boron-dipyrrin chromophores containing a 5-aryl group with or without internal steric hindrance toward aryl rotation have been synthesized and then characterized via X-ray diffraction, static and time-resolved optical spectroscopy, and theory. Compounds with a 5-phenyl or 5-(4-tert-butylphenyl) group show low fluorescence yields (similar to 0.06) and short excited-singlet-state lifetimes (similar to 500 ps), and decay primarily (> 90%) by nonradiative internal conversion to the ground state. In contrast, sterically hindered analogues having an o-tolyl or mesityl group at the 5-position exhibit high fluorescence yields (similar to 0.9) and long excited-state lifetimes (similar to 6 ns). The X-ray structures indicate that the phenyl or 4-tert-butylphenyl ring lies at an angle of similar to 60 degrees with respect to the dipyrrin framework whereas the angle is similar to 80 degrees for mesityl or o-tolyl groups. The calculated potential energy surface for the phenyl-substituted complex indicates that the excited state has a second, lower energy minimum in which the nonhindered aryl ring rotates closer to the mean plane of the dipyrrin, which itself undergoes some distortion. This relaxed, distorted excited-state conformation has low radiative probability as well as a reduced energy gap from the ground state supporting a favorable vibrational overlap factor for nonradiative deactivation. Such a distorted conformation is energetically inaccessible in a complex bearing the sterically hindered o-tolyl or mesityl group at the 5-position, leading to a high radiative probability involving conformations at or near the initial Franck-Condon form of the excited state. These combined results demonstrate the critical role of aryl-ring rotation in governing the excited-state dynamics of this class of widely used dyes.

  DOI：

  10.1021/jp0525078