5-(1,3,5,7-tetramethyl-2,6-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indaceno)-5'-methyl-2,2'-bipyridine | 1262393-04-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 5-(1,3,5,7-tetramethyl-2,6-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indaceno)-5'-methyl-2,2'-bipyridine
• 英文别名: Eistl01；5,11-diethyl-2,2-difluoro-4,6,10,12-tetramethyl-8-[2-(4-methylpyridin-2-yl)pyridin-4-yl]-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• CAS: 1262393-04-3
• 化学式: C₂₈H₃₁BF₂N₄
• 分子量: 472.389
• InChiKey: GSZLIRNAOZRDFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  35
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  33.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dichlorobis(dimethyl sulfoxide)platinum(II) 、 5-(1,3,5,7-tetramethyl-2,6-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indaceno)-5'-methyl-2,2'-bipyridine 以 甲苯 为溶剂， 以84%的产率得到[PtCl2(5-(1,3,5,7-tetramethyl-2,6-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indaceno)-5'-methyl-2,2'-bipyridine)]
  参考文献：
  名称：

  Sensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy−Pt(II)(diimine)(dithiolate) Conjugates

  摘要：

  The dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV-vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based (1)pi pi* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based (MML)-M-1'CT (mixed metal-ligand to ligand charge transfer) excited state (tau(3)(SEnT) = 0.6 ps, tau(4)(SEnT) = 0.5 ps, and tau(6)(SEnT) = 1.6 ps), which undergoes rapid intersystem crossing to the (MMLL)-M-3'CT state due to the heavy Pt(II) ion. The (MMLL)-M-3'CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based 3 pi pi* excited state (tau(3)(TEnT) = 8.2 ps, tau(4)(TEnT) = 5 ps, and tau(6)(TEnT) = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.

  DOI：

  10.1021/ja1070366
• 作为产物：
  描述：

  2,4-二甲基-3-乙基吡咯 在 三氟化硼乙醚 、 三乙胺 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 133.0h， 生成 5-(1,3,5,7-tetramethyl-2,6-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indaceno)-5'-methyl-2,2'-bipyridine
  参考文献：
  名称：

  Sensitizing the Sensitizer: The Synthesis and Photophysical Study of Bodipy−Pt(II)(diimine)(dithiolate) Conjugates

  摘要：

  The dyads 3, 4, and 6, combining the Bodipy chromophore with a Pt(bpy)(bdt) (bpy = 2,2'-bipyridine, bdt = 1,2-benzenedithiolate, 3 and 6) or a Pt(bpy)(mnt) (mnt = maleonitriledithiolate, 4) moiety, have been synthesized and studied by UV-vis steady-state absorption, transient absorption, and emission spectroscopies and cyclic voltammetry. Comparison of the absorption spectra and cyclic voltammograms of dyads 3, 4, and 6 and those of their model compounds 1a, 2, 5, and 7 shows that the spectroscopic and electrochemical properties of the dyads are essentially the sum of their constituent chromophores, indicating negligible interaction of the constituent chromophores in the ground state. However, emission studies on 3 and 6 show a complete absence of both Bodipy-based fluorescence and the characteristic luminescence of the Pt(bpy)(bdt) unit. Dyad 4 shows a weak Pt(mnt)-based emission. Transient absorption studies show that excitation of the dyads into the Bodipy-based (1)pi pi* excited state is followed by singlet energy transfer (SEnT) to the Pt(dithiolate)-based (MML)-M-1'CT (mixed metal-ligand to ligand charge transfer) excited state (tau(3)(SEnT) = 0.6 ps, tau(4)(SEnT) = 0.5 ps, and tau(6)(SEnT) = 1.6 ps), which undergoes rapid intersystem crossing to the (MMLL)-M-3'CT state due to the heavy Pt(II) ion. The (MMLL)-M-3'CT state is then depopulated by triplet energy transfer (TEnT) to the low-lying Bodipy-based 3 pi pi* excited state (tau(3)(TEnT) = 8.2 ps, tau(4)(TEnT) = 5 ps, and tau(6)(TEnT) = 160 ps). The transition assignments are supported by TD-DFT calculations. Both energy-transfer processes are shown to proceed via a Dexter electron exchange mechanism. The much longer time constants for dyad 6 relative to 3 are attributed to the significantly poorer coupling and resonance of charge-separated species that are intermediates in the electron exchange process.

  DOI：

  10.1021/ja1070366

文献信息

• Development of Bodipy-Ir complex as an near-infrared photosensitizer for photoacoustic imaging-guided photodynamic therapy
  作者：Chuangjun Liu、Yingchun Jiang、Jingjing Xiang、Chunbai Xiang、Hongfeng Li、Huacheng Li、Fangfang Wei、Jiahao Huang、Rongqiang Li、Keith Man-Chung Wong、Ping Gong

  DOI：10.1016/j.dyepig.2022.110900

  日期：2023.1